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Sample records for supercritical methanol electronic

  1. Depolymerization of polyethylene terephthalate in supercritical methanol

    Science.gov (United States)

    Goto, Motonobu; Koyamoto, Hiroshi; Kodama, Akio; Hirose, Tsutomu; Nagaoka, Shoji

    2002-11-01

    The degradation of polyethylene terephthalate (PET) in supercritical methanol was investigated with the aim of developing a process for chemical recycling of waste plastics. A batch reactor was used at temperatures of 573-623 K under an estimated pressure of 20 MPa for a reaction time of 2-120 min. PET was decomposed to its monomers, dimethyl terephthalate and ethylene glycol, by methanolysis in supercritical methanol. The reaction products were analysed using size-exclusion chromatography, gas chromatography-mass spectrometry, and reversed-phase liquid chromatography. The molecular weight distribution of the products was obtained as a function of reaction time. The yields of monomer components of the decomposition products including by-products were measured. Continuous kinetics analysis was performed on the experimental data.

  2. Performance of supercritical methanol in polyurethane degradation

    Directory of Open Access Journals (Sweden)

    Liu Lu

    2016-01-01

    Full Text Available Polyurethane is a group of block copolymer which is composed of diisocyanate, chain extender, and polyol, including polyurethane foam, polyurethane elastomer, waterborne polyurethane, etc. This research focused on thermoplastic polyurethane elastomer (TPU which is formed with 4,4’-diphenylmethane diisocyanate (MDI, poly(1,4-butanediol-hexanedioic acid diolpolyester(PBA and extended with 1,4-butanediol(BDO.The degradation of TPU was carried out with the help of methanol as the supercritical solvent. The SEM of the reaction residues revealed the process of the depolymerisation. The products were measured by GC-MS and found out to be PBA, BDO and 4,4’-methylene diphenyl carbamate(MDC which is themethylate of MDI.GC-FID, HPLC-UV and GPC were used to further analysis. The experimental results showed that supercritical methanol performed outstandingly in TPU recycling, it needed lower temperature and shorter time than regular methods. At 230°C/70min, over 90% raw materials of TPU could be recovered.

  3. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol

    Energy Technology Data Exchange (ETDEWEB)

    Saka, S.; Kusdiana, D. [Kyoto University, Kyoto (Japan). Dept. of Socio-Environmental Energy Science, Graduate School of Energy Science

    2001-01-01

    Transesterification reaction of rapeseed oil in supercritical methanol was investigated without using any catalyst. An experiment has been carried out in the batch-type reaction vessel preheated at 350 and 400{degree}C and at a pressure of 45-65 MPa, and with a molar ratio of 1:42 of the rapeseed oil to methanol. It was consequently demonstrated that, in a preheating temperature of 350{degree}C, 240 s of supercritical treatment of methanol was sufficient to convert the rapeseed oil to methyl esters and that, although the prepared methyl esters were basically the same as those of the common method with a basic catalyst, the yield of methyl esters by the former was found to be higher than that by the latter. In addition, it was found that this supercritical methanol process requires the shorter reaction time and simpler purification procedure because of the unused catalyst. 16 refs., 9 figs., 2 tabs.

  4. Reactions of supercritical water and supercritical methanol with benzaldehyde; Chorinkaisui oyobi chorinkai methanol to benzaldehyde tono hanno

    Energy Technology Data Exchange (ETDEWEB)

    Yokoyama, C.; Yasuda, T.; Nishi, K.; Takahashi, S. [Tohoku University, Sendai (Japan). Institute for Chemical Reaction Science

    1996-11-01

    The reactions of supercritical water and supercritical methanol with benzaldehyde have been examined in the temperature range from 553 to 693 K, and the reaction pathways have been examined from the temporal variations of the reaction products. For the reaction of benzaldehyde with supercritical water, the major product was benzene, which was formed from the pyrolysis of benzaldehyde. The benzoic acid and benzyl alcohol were the by-products, produced from the Cannizzaro-type disproportionation reaction of benzaldehyde with the hydrate formed from the reaction with water and benzaldehyde. The major product for the reaction of benzaldehyde with supercritical methanol was benzyl alcohol, and the by-product were dimethylacetal, benzene, and methyl benzoic acid. Under the reaction conditions of this study, a significant amount of acetal was produced from benzaldehyde and methanol. The pyrolysis of acetal yielded benzyl alcohol. 29 refs., 6 figs., 4 tabs.

  5. Reforming of methanol and glycerol in supercritical water

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Assink, D.; Heeres, H. J.

    2011-01-01

    Reforming of pure glycerol, crude glycerin, and methanol (pure and in the presence of Na(2)CO(3)) in supercritical water was investigated. Continuous experiments were carried out at temperatures between 450 and 650 degrees C, residence times between 6 and 173 s, and feed concentrations of 3-20 wt%.

  6. Biodiesel Production from Acidified Oils via Supercritical Methanol

    Directory of Open Access Journals (Sweden)

    Jianxin Li

    2011-12-01

    Full Text Available In biodiesel production, the vegetable oil used as raw material for transesterification should be free of water and free fatty acids (FFAs, which may consume catalyst and reduce catalyst efficiency. In this work biodiesel was prepared from acidified oils (AO through a supercritical methanol route, in which the esterification of FFAs and transesterification of glyceride with methanol occurred simultaneously. The effects of the mass ratio of methanol to AO, the operation temperature as well as the water content on the FFAs conversion and glycerol yield were investigated. The results indicated that the FFAs conversion for esterification under the condition of 1:1 methanol/oil ratio, 310 °C and 15 min reaction time reached 98.7%, and the glycerol yield for transesterification under 0.25:1 methanol/oil ratio, 290 °C and 20 min reaction time reached 63.5% respectively.

  7. Biodiesel production from rice bran oil and supercritical methanol.

    Science.gov (United States)

    Kasim, Novy Srihartati; Tsai, Tsung-Han; Gunawan, Setiyo; Ju, Yi-Hsu

    2009-04-01

    In this study, production of biodiesel from low cost raw materials, such as rice bran and dewaxed-degummed rice bran oil (DDRBO), under supercritical condition was carried out. Carbon dioxide (CO2) was employed as co-solvent to decrease the supercritical temperature and pressure of methanol. The effects of different raw materials on the yield of biodiesel production were investigated. In situ transesterification of rice bran with supercritical methanol at 30MPa and 300 degrees C for 5 min was not a promising way to produce biodiesel because the purity and yield of fatty acid methyl esters (FAMEs) obtained were 52.52% and 51.28%, respectively. When DDRBO was reacted, the purity and yield were 89.25% and 94.84%, respectively. Trans-FAMEs, which constituted about 16% of biodiesel, were found. They were identified as methyl elaidate [trans-9], methyl linoleaidate [trans-9, trans-12], methyl linoleaidate [cis-9, trans-12], and methyl linoleaidate [trans-9, cis-12]. Hydrocarbons, which constituted about 3% of the reaction product, were also detected.

  8. TRANSESTERIFICATION OF VEGETABLES OIL USING SUBAND SUPERCRITICAL METHANOL

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    Nyoman Puspa Asri

    2012-11-01

    Full Text Available A benign process, non catalytic transesterification in sub and supercritical methanol method was usedto prepare biodiesel from vegetables oil. The experiment was carried out in batch type reactor (8.8 mlcapacity, stainless steel, AKICO, JAPAN by changing the reaction condition such as reactiontemperature (from 210°C in subcritical condition to 290°C in supercritical state with of 20°Cinterval, molar ratio oil to methanol (1:12-1:42 and time of reaction (10-90 min. The fatty acidmethyl esters (FAMEs content was analyzed by gas chromatography-flame ionization detector (GCFID.Such analysis can be used to determine the biodiesel yield of the transesterification. The resultsshowed that the yield of biodiesel increases gradually with the increasing of reaction time atsubcritical state (210-230oC. However, it was drastically increased at the supercritical state (270-290oC. Similarly, the yield of biodiesel sharply increased with increasing the ratio molar of soy oilmethanolup to 1:24. The maximum yield 86 and 88% were achieved at 290oC, 90 min of reaction timeand molar ratio of oil to methanol 1:24, for soybean oil and palm oil, respectively.Proses transesterifikasi non katalitik dengan metanol sub dan superkritis,merupakan proses yang ramah lingkungan digunakan untuk pembuatan biodiesel dari minyak nabati.Percobaan dilakukan dalam sebuah reaktor batch (kapasitas 8,8 ml, stainless steel, AKICO, JAPAN,dengan variabel kondisi reaksi seperti temperatur reaksi (dari kondisi subkritis 210°C-kondisisuperkritis 290°C dengan interval 20°C, rasio molar minyak-metanol (1:12-1:42 dan waktu reaksi(10-90 menit. Kandungan metil ester asam lemak (FAME dianalisis dengan kromatografi gasdengan detektor FID (GC-FID. Hasil Analisis tersebut dapat digunakan untuk menentukan yieldbiodiesel dari proses transesterifikasi. Hasil penelitian menunjukkan bahwa yield biodiesel meningkatsecara perlahan dengan meningkatnya waktu reaksi pada keadaan subkritis (210-230oC. Namun

  9. Transesterification of rapeseed oil in supercritical methanol in a flow reactor

    Science.gov (United States)

    Anikeev, V. I.; Yakovleva, E. Yu.

    2012-11-01

    Transesterification reactions of rapeseed oil in supercritical methanol in a flow reactor over a wide range of variation of the methanol/oil ratio, pressure, and contact time are studied. Conditions ensuring selectivity and a high degree of rapeseed oil conversion are found. Experiments to study this reaction in the presence of zeolite heterogeneous catalyst are performed.

  10. Solvent adsorption in SFC : Adsorption of methanol under supercritical conditions

    OpenAIRE

    Edström, Emelie

    2015-01-01

    Chromatography is a widely used separation technique including many different modes, for example supercritical fluid chromatography (SFC) which uses a supercritical fluid as mobile phase. A supercritical fluid is achieved when a substance is subjected to a temperature and pressure above the critical point and the boundary between the liquid phase and gas phase is erased. The interest for SFC has increased in recent years, mainly for separation of chiral molecules in the pharmaceutical industr...

  11. A closer study of methanol adsorption and its impact on solute retentions in supercritical fluid chromatography.

    Science.gov (United States)

    Glenne, Emelie; Öhlén, Kristina; Leek, Hanna; Klarqvist, Magnus; Samuelsson, Jörgen; Fornstedt, Torgny

    2016-04-15

    Surface excess adsorption isotherms of methanol on a diol silica adsorbent were measured in supercritical fluid chromatography (SFC) using a mixture of methanol and carbon dioxide as mobile phase. The tracer pulse method was used with deuterium labeled methanol as solute and the tracer peaks were detected using APCI-MS over the whole composition range from neat carbon dioxide to neat methanol. The results indicate that a monolayer (4Å) of methanol is formed on the stationary phase. Moreover, the importance of using the set or the actual methanol fractions and volumetric flows in SFC was investigated by measuring the mass flow respective pressure and by calculations of the actual volume fraction of methanol. The result revealed a significant difference between the value set and the actually delivered volumetric methanol flow rate, especially at low modifier fractions. If relying only on the set methanol fraction in the calculations, the methanol layer thickness should in this system be highly overestimated. Finally, retention times for a set of solutes were measured and related to the findings summarized above concerning methanol adsorption. A strongly non-linear relationship between the logarithms of the retention factors and the modifier fraction in the mobile phase was revealed, prior to the established monolayer. At modifier fractions above that required for establishment of the methanol monolayer, this relationship turns linear which explains why the solute retention factors are less sensitive to changes in modifier content in this region.

  12. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

    NARCIS (Netherlands)

    Warner, Genoa; Hansen, Thomas S; Riisager, Anders; Beach, Evan S; Barta, Katalin; Anastas, Paul T

    An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin

  13. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol

    DEFF Research Database (Denmark)

    Hansen, Thomas Søndergaard; Barta, Katalin; Anastas, Paul T.

    2012-01-01

    Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions...

  14. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

    NARCIS (Netherlands)

    Warner, Genoa; Hansen, Thomas S; Riisager, Anders; Beach, Evan S; Barta, Katalin; Anastas, Paul T

    2014-01-01

    An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin co

  15. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol

    NARCIS (Netherlands)

    Hansen, Thomas S.; Barta, Katalin; Anastas, Paul T.; Ford, Peter C.; Riisager, Anders

    2012-01-01

    Catalytic conversion of HMF to valuable chemicals was achieved over a Cu-doped porous metal oxide in supercritical methanol. The hydrotalcite catalyst precursor is prepared following simple synthetic procedures, using inexpensive and earth-abundant starting materials in aqueous solutions. The hydrog

  16. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

    NARCIS (Netherlands)

    Warner, Genoa; Hansen, Thomas S; Riisager, Anders; Beach, Evan S; Barta, Katalin; Anastas, Paul T

    2014-01-01

    An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin co

  17. A comparative study of biodiesel production using methanol, ethanol, and tert-butyl methyl ether (MTBE) under supercritical conditions.

    Science.gov (United States)

    Farobie, Obie; Matsumura, Yukihiko

    2015-09-01

    In this study, biodiesel production under supercritical conditions among methanol, ethanol, and tert-butyl methyl ether (MTBE) was compared in order to elucidate the differences in their reaction behavior. A continuous reactor was employed, and experiments were conducted at various reaction temperatures (270-400 °C) and reaction times (3-30 min) and at a fixed pressure of 20 MPa and an oil-to-reactant molar ratio of 1:40. The results showed that under the same reaction conditions, the supercritical methanol method provided the highest yield of biodiesel. At 350 °C and 20 MPa, canola oil was completely converted to biodiesel after 10, 30, and 30 min in the case of - supercritical methanol, ethanol, and MTBE, respectively. The reaction kinetics of biodiesel production was also compared for supercritical methanol, ethanol, and MTBE.

  18. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol

    DEFF Research Database (Denmark)

    Warner, Genoa; Hansen, Thomas Søndergaard; Riisager, Anders

    2014-01-01

    conversion to methanol-soluble products, without char formation, were based on copper in combination with other dopants based on relatively earth-abundant metals. Nearly complete conversion of lignin to bio-oil composed of monomers and low-mass oligomers with high aromatic content was obtained in 6. h at 310......An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin...

  19. Biodiesel Production Using Supercritical Methanol with Carbon Dioxide and Acetic Acid

    Directory of Open Access Journals (Sweden)

    Chao-Yi Wei

    2013-01-01

    Full Text Available Transesterification of oils and lipids in supercritical methanol is commonly carried out in the absence of a catalyst. In this work, supercritical methanol, carbon dioxide, and acetic acid were used to produce biodiesel from soybean oil. Supercritical carbon dioxide was added to reduce the reaction temperature and increase the fats dissolved in the reaction medium. Acetic acid was added to reduce the glycerol byproduct and increase the hydrolysis of fatty acids. The Taguchi method was used to identify optimal conditions in the biodiesel production process. With an optimal reaction temperature of 280°C, a methanol-to-oil ratio of 60, and an acetic acid-to-oil ratio of 3, a 97.83% yield of fatty acid methyl esters (FAMEs was observed after 90 min at a reaction pressure of 20 MPa. While the common approach to biodiesel production results in a glycerol byproduct of about 10% of the yield, the practices reported in this research can reduce the glycerol byproduct by 30.2% and thereby meet international standards requiring a FAME content of >96%.

  20. Dynamics of supercritical methanol of varying density from first principles simulations: hydrogen bond fluctuations, vibrational spectral diffusion, and orientational relaxation.

    Science.gov (United States)

    Yadav, Vivek Kumar; Chandra, Amalendu

    2013-06-14

    A first principles study of the dynamics of supercritical methanol is carried out by means of ab initio molecular dynamics simulations. In particular, the fluctuation dynamics of hydroxyl stretch frequencies, hydrogen bonds, dangling hydroxyl groups, and orientation of methanol molecules are investigated for three different densities at 523 K. Apart from the dynamical properties, various equilibrium properties of supercritical methanol such as the local density distributions and structural correlations, hydrogen bonding aspects, frequency-structure correlations, and dipole distributions of methanol molecules are also investigated. In addition to the density dependence of various equilibrium and dynamical properties, their dependencies on dispersion interactions are also studied by carrying out additional simulations using a dispersion corrected density functional for all the systems. It is found that the hydrogen bonding between methanol molecules decreases significantly as we move to the supercritical state from the ambient one. The inclusion of dispersion interactions is found to increase the number of hydrogen bonds to some extent. Calculations of the frequency-structure correlation coefficient reveal that a statistical correlation between the hydroxyl stretch frequency and the nearest hydrogen-oxygen distance continues to exist even at supercritical states of methanol, although it is weakened with increase of temperature and decrease of density. In the supercritical state, the frequency time correlation function is found to decay with two time scales: One around or less than 100 fs and the other in the region of 250-700 fs. It is found that, for supercritical methanol, the times scales of vibrational spectral diffusion are determined by an interplay between the dynamics of hydrogen bonds, dangling OD groups, and inertial rotation of methanol molecules and the roles of these various components are found to vary with density of the supercritical solvent. Effects

  1. Methane and methanol oxidation in supercritical water: Chemical kinetics and hydrothermal flame studies

    Energy Technology Data Exchange (ETDEWEB)

    Steeper, R.R.

    1996-01-01

    Supercritical water oxidation (SCWO) is an emerging technology for the treatment of wastes in the presence of a large concentration of water at conditions above water`s thermodynamic critical point. A high-pressure, optically accessible reaction cell was constructed to investigate the oxidation of methane and methanol in this environment. Experiments were conducted to examine both flame and non-flame oxidation regimes. Optical access enabled the use of normal and shadowgraphy video systems for visualization, and Raman spectroscopy for in situ measurement of species concentrations. Flame experiments were performed by steadily injecting pure oxygen into supercritical mixtures of water and methane or methanol at 270 bar and at temperatures from 390 to 510{degrees}C. The experiments mapped conditions leading to the spontaneous ignition of diffusion flames in supercritical water. Above 470{degrees}C, flames spontaneously ignite in mixtures containing only 6 mole% methane or methanol. This data is relevant to the design and operation of commercial SCWO processes that may be susceptible to inadvertent flame formation. Non-flame oxidation kinetics experiments measured rates of methane oxidation in supercritical water at 270 bar and at temperatures from 390 to 442{degrees}C. The initial methane concentration was nominally 0.15 gmol/L, a level representative of commercial SCWO processes. The observed methane concentration histories were fit to a one-step reaction rate expression indicating a reaction order close to two for methane and zero for oxygen. Experiments were also conducted with varying water concentrations (0 to 8 gmol/L) while temperature and initial reactant concentrations were held constant. The rate of methane oxidation rises steadily with water concentration up to about 5 gmol/L and then abruptly falls off at higher concentrations.

  2. A New Process for Synthesis of Dimethyl Carbonate from Ethylene Carbonate and Methanol without any Catalyst under Supercritical Conditions

    Institute of Scientific and Technical Information of China (English)

    Xiu Juan FENG; Xiao Gang LI; Ren HE; Hui ZHOU

    2005-01-01

    Dimethyl carbonate was synthesized by transesterification reaction between ethylene carbonate and methanol under supercritical conditions without any catalyst. Experimental results showed that the residence time and the molar ratio of methanol to ethylene carbonate all can affect the conversion of ethylene carbonate. When the molar ratio of methanol to ethylene carbonate was 8:1, 81.2 % conversion can be achieved at 9.0 MPa and 250℃ after 8 h.

  3. Molecular Dynamics Simulation of Na(+)-Cl(-) Ion-Pair in Water-Methanol Mixtures under Supercritical and Ambient Conditions.

    Science.gov (United States)

    Keshri, Sonanki; Sarkar, Atanu; Tembe, B L

    2015-12-17

    Constrained molecular dynamics simulations have been performed to investigate the structure and thermodynamics of Na(+)-Cl(-) ion-pair association in water-methanol mixtures under supercritical and ambient conditions in dilute solutions. From the computed potentials of mean force (PMFs) we find that contact ion pairs (CIPs) are more stable than all other associated states of the ion pairs in both ambient and supercritical conditions. Stabilities of CIPs increase with increase in the mole fraction of methanol. In supercritical conditions, major changes in PMFs occur as we go from x(methanol) = 0.00 to x(methanol) = 0.50. The stable solvent shared ion pair (SShIP) which occurs in x(methanol) = 0.00 and 0.25, vanishes when x(methanol) is 0.50 or greater. The stabilities of these ion pairs increase with increasing temperature. Local structures around the ions are studied using the radial distribution functions, density profiles, angular distribution functions, running coordination numbers and excess coordination numbers. Preferential solvation analysis shows that both Na(+) and Cl(-) ions are preferentially solvated by water. From the calculation of enthalpies and entropies, we find that Na(+)-Cl(-) ion-pair association in water-methanol binary mixtures is endothermic and driven by entropy both in ambient as well as under supercritical conditions.

  4. Biodiesel II: A new concept of biodiesel production - transesterification with supercritical methanol

    Directory of Open Access Journals (Sweden)

    Skala Dejan U.

    2004-01-01

    Full Text Available Biodiesel is defined as a fuel that might be used as a pure biofuel or at high concentration in mineral oil derivatives, in accordance with specific quality standards for transport applications. The main raw material used for biodiesel production is rapeseed, which contains mono-unsaturated (about 60% and also, in a lower quantity, poly-unsaturated fatty acids (C 18:1 and C 18:3, as well as some amounts of undesired saturated fatty acids (palmitic and stearic acids. Other raw materials have also been used in the research and industrial production of biodiesel (palm-oil, sunflower-oil, soybean-oil, waste plant oil, animal fats, etc. The historical background of the biodiesel production, installed industrial capacities, as well as Directives of the European Parliament and of the Council (May 2003 regarding the promotion of the use of biofuels or other renewable fuels for transport are discussed in the first part of this article (Chem. Ind. 58 (2004. The second part focused on some new concepts and the future development of technology for biodiesel production based on the use of non-catalytic transesterification under supercritical conditions. A literature review, as well as original results based on the transesterification of animal fats, plant oil and used plant oil were discussed. Obtained results were compared with the traditional concept of transesterification based on base or acid catalysis. Experimental investigations of transesterification with supercritical methanol were performed in a 2 dm3 autoclave at 140 bar pressure and at 300°C with molar ratio of methanol to triglycerides of about 41. The degree of esterification strongly depends on the density of supercritical methanol and on the possibility of reaction occurring in one phase.

  5. Depolymerization of organosolv lignin using doped porous metal oxides in supercritical methanol.

    Science.gov (United States)

    Warner, Genoa; Hansen, Thomas S; Riisager, Anders; Beach, Evan S; Barta, Katalin; Anastas, Paul T

    2014-06-01

    An isolated, solvent-extracted lignin from candlenut (Aleurites moluccana) biomass was subjected to catalytic depolymerization in the presence of supercritical methanol, using a range of porous metal oxides derived from hydrotalcite-like precursors. The most effective catalysts in terms of lignin conversion to methanol-soluble products, without char formation, were based on copper in combination with other dopants based on relatively earth-abundant metals. Nearly complete conversion of lignin to bio-oil composed of monomers and low-mass oligomers with high aromatic content was obtained in 6h at 310°C using a catalyst based on a Cu- and La-doped hydrotalcite-like precursor. Product mixtures were characterized by NMR spectroscopy, gel permeation chromatography, and GC-MS.

  6. In-situ Transesterification of Jatropha curcas L. Seeds for Biodiesel Production using Supercritical Methanol

    Directory of Open Access Journals (Sweden)

    Ishak M.A.M.

    2017-01-01

    Full Text Available In-situ supercritical methanol transesterification for production of biodiesel from Jatropha curcas L. (JCL seeds was successfully being carried out via batch-wise reactor system, under varying temperatures of 180 - 300 °C, pressures of 6 - 18 MPa, reaction time of 5 - 35 min and seeds-to-methanol ratio of 1:15 - 1:45 (w/v. In this study, the extracted oil obtained showed the presence of FAME referring as biodiesel, indicating that transesterification reaction had occurred during the extraction process. The results showed that the biodiesel yield was obtained at optimum conditions of 280 °C, 12 MPa, 30 min and 1:40 (w/v were 97.9%.

  7. A whole biodiesel conversion process combining isolation, cultivation and in situ supercritical methanol transesterification of native microalgae.

    Science.gov (United States)

    Jazzar, Souhir; Quesada-Medina, Joaquín; Olivares-Carrillo, Pilar; Marzouki, Mohamed Néjib; Acién-Fernández, Francisco Gabriel; Fernández-Sevilla, José María; Molina-Grima, Emilio; Smaali, Issam

    2015-08-01

    A coupled process combining microalgae production with direct supercritical biodiesel conversion using a reduced number of operating steps is proposed in this work. Two newly isolated native microalgae strains, identified as Chlorella sp. and Nannochloris sp., were cultivated in both batch and continuous modes. Maximum productivities were achieved during continuous cultures with 318mg/lday and 256mg/lday for Chlorella sp. and Nannochloris sp., respectively. Microalgae were further characterized by determining their photosynthetic performance and nutrient removal efficiency. Biodiesel was produced by catalyst-free in situ supercritical methanol transesterification of wet unwashed algal biomass (75wt.% of moisture). Maximum biodiesel yields of 45.62wt.% and 21.79wt.% were reached for Chlorella sp. and Nannochloris sp., respectively. The analysis of polyunsaturated fatty acids of Chlorella sp. showed a decrease in their proportion when comparing conventional and supercritical transesterification processes (from 37.4% to 13.9%, respectively), thus improving the quality of the biodiesel.

  8. Noncatalytic mono-N-methylation of aniline in supercritical methanol: the kinetics and acid/base effect.

    Science.gov (United States)

    Takebayashi, Yoshihiro; Morita, Yoshinori; Sakai, Hideki; Abe, Masahiko; Yoda, Satoshi; Furuya, Takeshi; Sugeta, Tsutomu; Otake, Katsuto

    2005-08-21

    Aniline is easily N-methylated in supercritical methanol without catalyst at 350 degrees C and 0.237 g cm-3 to give mono-N-methylaniline with high selectivity, and the reaction rate is increased by a small amount of base (LiOH, NaOH, KOH, and CH3ONa), indicating a difference in the reaction mechanism from the ordinary acid-catalyzed one.

  9. Effect of CO2/N2 addition to supercritical methanol on reactivities and fuel qualities in biodiesel production

    OpenAIRE

    Imahara, Hiroaki; Xin, Jiayu; Saka, Shiro

    2009-01-01

    Addition of the third component to supercritical methanol has been studied in the literature for biodiesel production in order to reduce reaction temperature without deteriorating the reaction rate. However, effect of pressure had often been neglected in the discussion. In this paper, therefore, effect of pressure was examined with hexane, carbon dioxide (CO2) and nitrogen (N2) as one of the third components, using batch-type and flow-type reactors. As a result, it was found that an addition ...

  10. Comparison of large scale purification processes of naproxen enantiomers by chromatography using methanol-water and methanol-supercritical carbon dioxide mobile phases.

    Science.gov (United States)

    Kamarei, Fahimeh; Vajda, Péter; Guiochon, Georges

    2013-09-20

    This paper compares two methods used for the preparative purification of a mixture of (S)-, and (R)-naproxen on a Whelk-O1 column, using either high performance liquid chromatography or supercritical fluid chromatography. The adsorption properties of both enantiomers were measured by frontal analysis, using methanol-water and methanol-supercritical carbon dioxide mixtures as the mobile phases. The measured adsorption data were modeled, providing the adsorption isotherms and their parameters, which were derived from the nonlinear fit of the isotherm models to the experimental data points. The model used was a Bi-Langmuir isotherm, similar to the model used in many enantiomeric separations. These isotherms were used to calculate the elution profiles of overloaded elution bands, assuming competitive Bi-Langmuir behavior of the two enantiomers. The analysis of these profiles provides the basis for a comparison between supercritical fluid chromatographic and high performance liquid chromatographic preparative scale separations. It permits an illustration of the advantages and disadvantages of these methods and a discussion of their potential performance.

  11. Fuel Characteristics of Biodiesel Produced from a High-Acid Oil from Soybean Soapstock by Supercritical-Methanol Transesterification

    Directory of Open Access Journals (Sweden)

    Yi-Wei Lin

    2012-07-01

    Full Text Available A supercritical methanol transesterification method was applied to produce biodiesel from the high-acid oil of soybean soapstock. The fuel properties of biodiesel produced with various molar ratios of methanol to raw oil were analyzed and compared in this experimental study. Oleic acid (C18:1, linoleic acid (C18:2, and palmitic acid (C16:0 were the three main compounds in the high-acid oil-biodiesel. The saturated fatty acid content of the high-acid oil increased significantly due to the supercritical-methanol transesterification reaction. The fuel characteristics of the resulting high-acid oil, including the specific gravity and kinematic viscosity, were also greatly improved. The saturated fatty acid content of the biodiesel produced from the high-acid oil was higher than that of biodiesel from waste cooking oil produced by the subcritical transesterification using a strongly alkaline catalyst. The high-acid oil-biodiesel that was produced with a molar ratio of methanol to raw oil of 42 had the best fuel properties, including a higher distillation temperature and cetane index and a lower kinematic viscosity and water content, among the biodiesels with different molar ratios.

  12. Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study

    Directory of Open Access Journals (Sweden)

    Nyoman Puspa Asri

    2013-03-01

    Full Text Available Non catalytic transesterification in sub and supercritical methanol have been used to produce biodiesel from palm oil and soybean oil. A kinetic study was done under reaction condition with temperature and time control. The experiments were carried out in a batch type reactor at reaction temperatures from 210 °C (subcritical condition to 290 °C (the supercritical state in the interval ranges of temperature of 20 °C and at various molar ratios of oil to methanol. The rate constants of the reaction were determined by employing a simple method, with the overall chemical reaction followed the pseudo-first–order reaction. Based on the results, the rate constants of vegetables oil were significantly influenced by reaction temperature, which were gradually increased at subcritical temperature, but sharply increased in the supercritical state. However, the rate constants of soybean oil were slightly higher than that of palm oil. The activation energy for transesterification of soybean oil was 89.32 and 79.05 kJ/mole for palm oil. Meanwhile, the frequency factor values of both oils were 72462892 and 391210 min-1, respectively. The rate reaction for both of oil were expressed as -rTG = 72462892 exp(-89.32/RTCTG for soybean oil and -rTG = 391210 exp(-79.05/RTCTG for palm oil. © 2013 BCREC UNDIP. All rights reservedReceived: 18th October 2012; Revised: 14th December 2012; Accepted: 16th December 2012[How to Cite: N.P. Asri, S. Machmudah, W. Wahyudiono, S. Suprapto, K. Budikarjono, A. Roesyadi, M. Goto, (2013. Non Catalytic Transesterification of Vegetables Oil to Biodiesel in Sub-and Supercritical Methanol: A Kinetic’s Study. Bulletin of Chemical Reaction Engineering & Catalysis, 7 (3: 215-223. (doi:10.9767/bcrec.7.3.4060.215-223][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.7.3.4060.215-223 ] View in  |

  13. Substantial rate enhancements of the esterification reaction of phthalic anhydride with methanol at high pressure and using supercritical CO2 as a co-solvent in a glass microreactor

    NARCIS (Netherlands)

    Benito-Lopez, F.; Tiggelaar, Roald M.; Salblut, K.; Huskens, Jurriaan; Egberink, Richard J.M.; Reinhoudt, David; Gardeniers, Johannes G.E.; Verboom, Willem

    2007-01-01

    The esterification reaction of phthalic anhydride with methanol was performed at different temperatures in a continuous flow glass microreactor at pressures up to 110 bar and using supercritical CO2 as a co-solvent. The design is such that supercritical CO2 can be generated inside the microreactor.

  14. The study of correlations between hydrogen bonding characteristics in liquid, sub- and supercritical methanol. Molecular dynamics simulations and Raman spectroscopy analysis.

    Science.gov (United States)

    idrissi, Abdenacer; Oparin, Roman D; Krishtal, Sergey P; Krupin, Sergey V; Vorobiev, Evgeny A; Frolov, Andrey I; Dubois, Leo; Kiselev, Mikhail G

    2013-01-01

    Molecular dynamics (MD) studies of hydrogen bonding (H-bonding) in liquid, sub- and supercritical methanol have been performed in a wide range of thermodynamic parameters of state, using various potential models and two H-bond criteria. It was shown that there is the universal correlation between the average number of H-bonds per molecule (n(HB)) and the mole fraction of H-bonded molecules (X(HB)) for the studied thermodynamic parameters of state. The same feature was observed for the correlations between fractions of molecules forming one (f1), two (f2), three (f3) H-bonds and X(HB). These correlations served to fit experimental Raman spectra of methanol recorded under sub- and supercritical conditions. The advantage of the approach used here is that f1, f2, f3 values have a clear physical meaning and are dependent on the values of state parameters.

  15. Continuous esterification of free fatty acids in crude biodiesel by an integrated process of supercritical methanol and sodium methoxide catalyst.

    Science.gov (United States)

    Zeng, Dan; Li, Ruosong; Feng, Mingjun; Fang, Tao

    2014-10-01

    An integrated process of supercritical methanol (SCM) and sodium methoxide catalyst was developed to produce fatty acid methyl esters (FAMEs) via continuous esterification from crude biodiesel. The crude biodiesel with high free fatty acid (FFA) content must be refined to reduce the acid value (AV) for meeting the quality standards. The process parameters were studied by Box-Behnken design (BBD) of response surface methodology (RSM). The experimental results revealed that the AV of crude biodiesel decreased from 18.66 to 0.55 mg KOH g(-1) at the reaction conditions of 350 °C, 0.5 % amount of sodium methoxide catalyst, and 10 MPa. Temperature shows the most significant effect on the esterification, followed by pressure and amount of sodium methoxide catalyst. This integrated process proved to be a potential route to refine the crude biodiesel because of its continuity, high efficiency, and less energy consumption with relatively moderate reaction conditions compared with conventional methods.

  16. A novel recovery method of copper from waste printed circuit boards by supercritical methanol process: Preparation of ultrafine copper materials.

    Science.gov (United States)

    Xiu, Fu-Rong; Weng, Huiwei; Qi, Yingying; Yu, Gending; Zhang, Zhigang; Zhang, Fu-Shen; Chen, Mengjun

    2017-02-01

    In this study, supercritical methanol (SCM) process was successfully used for the preparation of ultrafine copper materials from waste printed circuit boards (PCBs) after nitric acid pretreatment. Waste PCBs were pretreated twice in nitric acid. Sn and Pb were recovered by the first nitric acid pretreatment. The leach liquor with a high concentration of copper ions after the second nitric acid leaching was subjected to SCM process. The mixture of Cu and Cu2O with poor uniformity of particle size was formed due to the effect of ferric iron contained in the leach liquor of waste PCBs, while more uniform and spherical Cu particles with high monodispersity and smaller size could be prepared after the removal of Fe. The size of Cu particles increased obviously with the decline of SCM temperature, and particles became highly aggregated when the reaction temperature decreased to 300°C. The size of Cu particles decreased markedly with the decrease of initial concentration of copper ion in the leach liquor of waste PCBs. It is believed that the process developed in this study is simple and practical for the preparation of ultrafine copper materials from waste PCBs with the aim of recycling these waste resources as a high value-added product. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Optimization of supercritical methanol reactive extraction by response surface methodology and product characterization from Jatropha curcas L. seeds.

    Science.gov (United States)

    Lim, Steven; Lee, Keat Teong

    2013-08-01

    In this study, optimization of supercritical reactive extraction directly from Jatropha seeds in a high pressure batch reactor using Response Surface Methodology (RSM) coupled with Central Composite Rotatable Design (CCRD) was performed. Four primary variables (methanol to solid ratio (SSR), reaction temperature, time and CO2 initial pressure) were investigated under the proposed constraints. It was found that all variables had significant effects towards fatty acid methyl esters (FAME) yield. Moreover, three interaction effects between the variables also played a major role in influencing the final FAME yield. Optimum FAME yield at 92.0 wt.% was achieved under the following conditions: 5.9 SSR, 300°C, 12.3 min and 20 bar CO2. Final FAME product was discovered to fulfil existing international standard. Preliminary characterization analysis proved that the solid residue can be burnt as solid fuel in the form of biochar while the liquid product can be separated as specialty chemicals or burned as bio-oil for energy production. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Self-diffusion measurements of methanol and 1-decanol in supercritical CO{sub 2} by {sup 13}C pulsed field gradient NMR

    Energy Technology Data Exchange (ETDEWEB)

    Bai, S.; Mayne, C.L.; Grant, D.M. [Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemistry; Taylor, C.M.V. [Los Alamos National Lab., NM (United States). Organic Analytical Chemistry Group

    1997-10-01

    A small amount of a highly polar compound, such as methanol, is frequently added to supercritical fluid (SCF) carbon dioxide to enhance its ability to dissolve polar molecules in SCF separation technology. Few diffusion coefficients in SCF mixtures have been reported in the literature. The pulsed field gradient spin-echo technique (PGSE) has been used extensively to measure self-diffusion in neat monohydric alcohols under pressure. Hurle et al. and Luedemann et al. showed that the experimental diffusion coefficients of methanol may be explained by a rough hard-sphere model (RHS) with a roughness parameter, A. In this paper, diffusion measurements are reported for CO{sub 2}-methanol and CO{sub 2}-decanol mixtures in supercritical fluids. Since methanol in CO{sub 2} is primarily monomeric at low concentration, the RHS model, that is accurate for most simple, non-associated liquids, should apply. Previous nuclear spin-lattice relaxation studies in SCF CO{sub 2} suggest a large local solvent density enhancement, or solvent clustering, near a alcohol solute molecule under SCF conditions. If solvent clustering occurs in the vicinity of alcohol solute molecules, it should affect the diffusion coefficients. The authors have made the requisite measurements and found that they corroborate their previous spin-relaxation data.

  19. Direct Methanol Fuel Cell Prototype Demonstration for Consumer Electronics Applications

    Energy Technology Data Exchange (ETDEWEB)

    Carlstrom, Charles, M., Jr.

    2009-07-07

    This report is the final technical report for DOE Program DE-FC36-04GO14301 titled “Direct Methanol Fuel Cell Prototype Demonstration for Consumer Electronics Applications”. Due to the public nature of this report some of the content reported in confidential reports and meetings to the DOE is not covered in detail in this report and some of the content has been normalized to not show actual values. There is a comparison of the projects accomplishments with the objectives, an overview of some of the key subsystem work, and a review of the three levels of prototypes demonstrated during the program. There is also a description of the eventual commercial product and market this work is leading towards. The work completed under this program has significantly increased the understanding of how Direct Methanol Fuel Cells (DMFC) can be deployed successfully to power consumer electronic devices. The prototype testing has demonstrated the benefits a direct methanol fuel cell system has over batteries typically used for powering consumer electronic devices. Three generations of prototypes have been developed and tested for performance, robustness and life. The technologies researched and utilized in the fuel cell stack and related subsystems for these prototypes are leveraged from advances in other industries such as the hydrogen fueled PEM fuel cell industry. The work under this program advanced the state of the art of direct methanol fuel cells. The system developed by MTI micro fuel cells aided by this program differs significantly from conventional DMFC designs and offers compelling advantages in the areas of performance, life, size, and simplicity. The program has progressed as planned resulting in the completion of the scope of work and available funding in December 2008. All 18 of the final P3 prototypes builds have been tested and the results showed significant improvements over P2 prototypes in build yield, initial performance, and durability. The systems have

  20. Methanol as an alternative electron donor in chain elongation for butyrate and caproate formation

    NARCIS (Netherlands)

    Chen, W.S.; Ye, Y.; Steinbusch, K.J.J.; Strik, D.P.B.T.B.; Buisman, C.J.N.

    2016-01-01

    Chain elongation is an emerging mixed culture biotechnology converting acetate into valuable biochemicals by using ethanol as an external electron donor. In this study we proposed to test another potential electron donor, methanol, in chain elongation. Methanol can be produced through the thermoc

  1. 亚/超临界甲醇体系中磷钼酸催化液化木粉%Catalytic liquefaction of wood in sub/supercritical methanol under phosphomolybdic acid

    Institute of Scientific and Technical Information of China (English)

    曾常伟; 林星; 汪雪琴; 蔡政汉; 吕建华; 黄彪

    2016-01-01

    To discover bio-environmental and sustainable catalyst to effectively transform fir sawdust to biofuel, liquefaction process catalyzed by phosphomolybdic acid and using sub/supercritical methanol as solvent was evaluated. The optimum reaction condition was investigated in terms of temperature, duration, dosages of catalyst and sawdust. Results showed that phosphomolybdic acid to-gether with subcritical methanol significantly accelerated sawdust liquefaction. The optimum reaction condition was achieved at liquif-ying 1 g sawdust, 150 mL methanol and 0.5 g phosphomolybdic acid at 240℃ for 30 minutes, maximizing at 93.32%. Subsequent-ly, quantity and chemical composition of light bio-oil, heavy bio-oil and residue were characterized by scanning electron microscope, Fourier translation infrared spectrum and gas chromatography-mass spectrometer. Results showed that the residue was mainly consist of lignin and its derivatives, which was from the liquefaction of lignin from methanol. Light bio-oil obtained at optimum condition comprised of complex compounds such as ester, phenol, aldehyde and ketone, resulting from the reaction between cellulose and methanol. While, heavy bio-oil, mainly comprised of phenol, was obtained from lignin liquefaction.%以杉木屑为原料,研究磷钼酸在亚/超临界甲醇条件下的催化液化性能,并探讨反应温度、反应时间、催化剂用量和杉木屑用量对杉木屑液化率的影响.结果表明该磷钼酸在亚/超临界甲醇条件下具有很好的催化液化性能.在150 mL甲醇、0.5 g催化剂、1 g杉木屑、240℃条件下反应30 min,液化率达到93.32%.采用SEM、FT-IR和GC-MS对液化残渣、轻油和重油进行表征.结果表明,残渣主要是由木质素或木质素衍生物组成;而液化产物轻油主要是由酯类、酚类、醛类、酮类等组成,主要是由纤维素及半纤维素与甲醇反应得到;而液化产物重油中的酚类物质主要是由木质素液化反应得到.

  2. Vapor–liquid equilibria of triglycerides–methanol mixtures and their influence on the biodiesel synthesis under supercritical conditions of methanol

    Directory of Open Access Journals (Sweden)

    ALEKSANDAR ORLOVIC

    2007-01-01

    Full Text Available The non-catalytic synthesis of biodiesel (fatty acids methyl esters from triglycerides and methanol proceeds at elevated pressures above 100 bar and temperatures above 523 K. Kinetic investigations of the system revealed an unusual behavior of the reaction rate constant with increasing temperature and pressure. In order to explain this phenomenon, the phase behavior of the triglycerides–methanol mixture was investigated. The phase equilibria of the binary system sunflower oil–methanol were measured at different temperatures between 473 and 503 K, and a range of pressures between 10 and 56 bar. The experimental data were correlated using the Peng–Robinson, Soave–Redlich–Kwong and Redlich–Kwong–Aspen equations of state and different mixing rules. The best results were obtained with the RK–ASPEN equation of state and the Van derWaals mixing rule (VdW, which were then used to calculate the distribution of the phases at pressures and temperatures usual for the non-catalytic synthesis of biodiesel under high pressures. The obtained data indicated a strong influence of the phase equilibria on the reaction kinetics.

  3. A first principles approach to the electronic properties of liquid and supercritical CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Cabral, Benedito J. Costa, E-mail: ben@cii.fc.ul.pt [Grupo de Física Matemática da Universidade de Lisboa, Av. Professor Gama Pinto 2, 1649-003 Lisboa (Portugal); Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa (Portugal); Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP (Brazil); Rivelino, Roberto [Instituto de Física da Universidade Federal da Bahia, Campus Universitário de Ondina, CEP 40210-340 Salvador, Bahia (Brazil); Coutinho, Kaline; Canuto, Sylvio [Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP (Brazil)

    2015-01-14

    The electronic absorption spectra of liquid and supercritical CO{sub 2} (scCO{sub 2}) are investigated by coupling a many-body energy decomposition scheme to configurations generated by Born-Oppenheimer molecular dynamics. A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies were calculated with time dependent density functional theory. A red-shift of ∼ 0.2 eV relative to the gas-phase monomer is observed for the first electronic absorption maximum in liquid and scCO{sub 2}. The origin of this shift, which is not very dependent on deviations from the linearity of the CO{sub 2} molecule, is mainly related to polarization effects. However, the geometry changes of the CO{sub 2} monomer induced by thermal effects and intermolecular interactions in condensed phase lead to the appearance of an average monomeric electric dipole moment 〈μ〉 = 0.26 ± 0.04 D that is practically the same at liquid and supercritical conditions. The predicted average quadrupole moment for both liquid and scCO{sub 2} is 〈Θ〉 = − 5.5 D Å, which is increased by ∼ −0.9 D Å relative to its gas-phase value. The importance of investigating the electronic properties for a better understanding of the role played by CO{sub 2} in supercritical solvation is stressed.

  4. A route to synthesis molybdenum disulfide-reduced graphene oxide (MoS2-RGO) composites using supercritical methanol and their enhanced electrochemical performance for Li-ion batteries

    Science.gov (United States)

    Choi, Mugyeom; Koppala, Siva Kumar; Yoon, Dohyeon; Hwang, Jieun; Kim, Seung Min; Kim, Jaehoon

    2016-03-01

    A simple and effective approach for the tight anchoring of molybdenum disulfide (MoS2) to the surface of supercritical-alcohol-reduced graphene oxide (SRGO) is developed. The MoS2-SRGO composites are synthesized by the one-pot deposition of MoO2 on SRGO and simultaneous reduction of GO to SRGO in supercritical methanol followed by sulfurization. The obtained MoS2-SRGO composites contain a crystalline MoS2 phase comprising 11-14 layers of MoS2. In addition, the composites have mesoporous structures with high porosities, ranging between 55 and 57%. In comparison with bare MoS2 and SRGO, the MoS2-SRGO composites have enhanced electrochemical performances due to their mesoporous structures and the synergetic effect between MoS2 and SRGO sheets. When tested as the anode in a secondary lithium battery, it shows high reversible capacity of 896 mAh g-1 at 50 mA g-1 after 50 cycles, a high rate capacity of 320 mAh g-1 at a high charge-discharge rate of 2.5 A g-1, and long-term cycling of 724 mAh g-1 at 50 mA g-1 after 200 cycles. This unique synthetic approach effectively and tightly anchors MoS2 nanoparticles to the SRGO surface, resulting in improved structural integrity, electron transfer efficiency between the SRGO sheets and MoS2, and Li-ion diffusion kinetics.

  5. Direct Electron Transfer of Methanol Dehydrogenase with Carbon Nanotubes

    OpenAIRE

    2009-01-01

    Modern day portable devices require ever increasing amount of energy. Fuel cells are one answer to demand for longer use times and quick recharge independent of an electric network. The use of hydrogen fuel cells for these kinds of applications has not been widespread, because storage of a required volume of hydrogen gas has been expensive or complicated. One solution to this is producing hydrogen in-situ from more easily storable compounds, e.g. methanol or ethanol. Reformers using inorganic...

  6. Electromagnetic waves and electron anisotropies downstream of supercritical interplanetary shocks

    CERN Document Server

    Wilson, L B; Szabo, A; Breneman, A; Cattell, C A; Goetz, K; Kellogg, P J; Kersten, K; Kasper, J C; Maruca, B A; Pulupa, M

    2012-01-01

    We present waveform observations of electromagnetic lower hybrid and whistler waves with f_ci 1.01. Thus, the whistler mode waves appear to be driven by a heat flux instability and cause perpendicular heating of the halo electrons. The lower hybrid waves show a much weaker correlation between \\partialB and normalized heat flux magnitude and are often observed near magnetic field gradients. A third type of event shows fluctuations consistent with a mixture of both lower hybrid and whistler mode waves. These results suggest that whistler waves may indeed be regulating the electron heat flux and the halo temperature anisotropy, which is important for theories and simulations of electron distribution evolution from the sun to the earth.

  7. Electron attachment to oxygen in supercritical hydrocarbon fluids

    Energy Technology Data Exchange (ETDEWEB)

    Nishikawa, M.; Holroyd, R.A.

    1983-10-15

    The rate of attachment of electrons to oxygen was studied in methane, ethane, and propane gas above the critical temperatures up to pressures of approx.200 atm. For all three gases, the rate increases with density and levels off above N = 3 x 10/sup 21/ molecules/cm/sup 3/. For ethane, there is little or no effect of temperature on the rate between 25 and 75 /sup 0/C and the rate is independent of electric field (E) up to E/N = 1.2 x 10/sup -18/ V cm/sup 2/, but increases at higher values of E/N. To explain the results, it is suggested that the energetics of the attachment reaction change with density; i.e., the energy level of the electron in the media (V/sub 0/) and the polarization energy (P/sup -/) of O/sub 2//sup -/ change with N. The rate of attachment increases with the energy term E/sub T/ = V/sub 0/-P/sup -/+E/sub k/, where E/sub k/ is the electron kinetic energy, similar to the way the attachment rate increases with electron kinetic energy in the dilute gas.

  8. Electron attachment to oxygen in supercritical hydrocarbon fluids

    Science.gov (United States)

    Nishikawa, Masaru; Holroyd, R. A.

    1983-10-01

    The rate of attachment of electrons to oxygen was studied in methane, ethane, and propane gas above the critical temperatures up to pressures of ˜200 atm. For all three gases, the rate increases with density and levels off above N=3×1021 molecules/cm3. For ethane, there is little or no effect of temperature on the rate between 25 and 75 °C and the rate is independent of electric field (E) up to E/N=1.2×10-18 V cm2, but increases at higher values of E/N. To explain the results, it is suggested that the energetics of the attachment reaction change with density; i.e., the energy level of the electron in the media (V0) and the polarization energy (P-) of O2- change with N. The rate of attachment increases with the energy term ET=V0-P-+Ek, where Ek is the electron kinetic energy, similar to the way the attachment rate increases with electron kinetic energy in the dilute gas.

  9. Bistable switching in supercritical n+-n-n+GaAs transferred electron devices

    DEFF Research Database (Denmark)

    Jøndrup, Peter; Jeppesen, Palle; Jeppson, Bert

    1976-01-01

    Bistable switching in supercritically doped n+-n-n+GaAs transferred electron devices (TED's) is investigated experimentally and interpreted in computer simulations, for which details of the computer program are given. Three switching modes all leading to stable anode domains are discussed, namely......: 1) cathode-triggered traveling domain; 2) cathode-triggered accumulation layer; 3) anode-triggered domain. Relative current drops up to 40 percent, and switching times down to 60 ps are obtained in low-duty-cycle pulsed experiments with threshold currents around 400 mA. Optimum device parameters...

  10. Supercritical instability of Dirac electrons in the field of two oppositely charged nuclei

    CERN Document Server

    Sobol, O O

    2016-01-01

    The Dirac equation for an electron in a finite dipole potential has been studied within the method of linear combination of atomic orbitals (LCAO). The Coulomb potential of the nuclei that compose a dipole is regularized, by considering the finite nuclear size. It is shown that if the dipole momentum reaches a certain critical value, the novel type of supercriticality occurs; namely, the wave function of the highest occupied electron bound state changes its localization from the negatively charged nucleus to the positively charged one. This phenomenon can be interpreted as a spontaneous creation of an electron-positron pair in vacuum, with each of the created particles being in the bound state with the corresponding nucleus and partially screening it.

  11. PtRu/C Electrocatalysts Prepared Using Gamma and Electron Beam Irradiation for Methanol Electrooxidation

    Directory of Open Access Journals (Sweden)

    Dionisio F. Silva

    2012-01-01

    Full Text Available PtRu/C electrocatalysts (carbon-supported PtRu nanoparticles were prepared in a single step submitting water/2-propanol mixtures containing Pt(IV and Ru(III ions and the carbon support to gamma and electron beam irradiation. The electrocatalysts were characterized by energy dispersive X-ray analysis (EDX, X-ray diffraction (XRD, transmission electron microscopy (TEM, and cyclic voltammetry and tested for methanol electrooxidation. PtRu/C electrocatalyst can be prepared in few minutes using high dose rate electron beam irradiation while using low dose rate gamma irradiation some hours were necessary to prepare it. The obtained materials showed the face-centered cubic (fcc structure of Pt and Pt alloys with average nanoparticle sizes of around 3 nm. The material prepared using electron beam irradiation was more active for methanol electrooxidation than the material prepared using gamma irradiation.

  12. Environmental Transmission Electron Microscopy of catalysts for the methanol synthesis

    DEFF Research Database (Denmark)

    Duchstein, Linus Daniel Leonhard

    Everywhere around the world, natural resources like crude oil are becoming less and harder to extract. It is therefore necessary to find alternatives to secure our future transportation in a sustainable way. This can be done e.g. through chemical conversion of lignocelluloses into bio-alcohol thr......Everywhere around the world, natural resources like crude oil are becoming less and harder to extract. It is therefore necessary to find alternatives to secure our future transportation in a sustainable way. This can be done e.g. through chemical conversion of lignocelluloses into bio...... atmosphere and temperature was investigated. CuNi was exposed to the electron beam for 3 different intensities and 3 different temperatures while the oxidation state of the Cu2+ was measured by energy electron loss spectroscopy. It turns out that the electron beam does have an influence but it does not seem...... to scale with the beam current density but foremost with the exposure time. The ETEM shows phase and chemical changes during the reaction....

  13. Modified Korteweg-de Vries solitons at supercritical densities in two-electron temperature plasmas

    CERN Document Server

    Verheest, Frank; Hereman, Willy A

    2016-01-01

    The supercritical composition of a plasma model with cold positive ions in the presence of a two-temperature electron population is investigated, initially by a reductive perturbation approach, under the combined requirements that there be neither quadratic nor cubic nonlinearities in the evolution equation. This leads to a unique choice for the set of compositional parameters and a modified Korteweg-de Vries equation (mKdV) with a quartic nonlinear term. The conclusions about its one-soliton solution and integrability will also be valid for more complicated plasma compositions. Only three polynomial conservation laws can be obtained. The mKdV equation with quartic nonlinearity is not completely integrable, thus precluding the existence of multi-soliton solutions. Next, the full Sagdeev pseudopotential method has been applied and this allows for a detailed comparison with the reductive perturbation results. This comparison shows that the mKdV solitons have slightly larger amplitudes and widths than those obta...

  14. Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

    Energy Technology Data Exchange (ETDEWEB)

    Frenzel, Johannes, E-mail: johannes.frenzel@theochem.rub.de; Marx, Dominik [Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum (Germany)

    2014-09-28

    Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partially hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are

  15. Methanol synthesis on ZnO(0001¯). IV. Reaction mechanisms and electronic structure.

    Science.gov (United States)

    Frenzel, Johannes; Marx, Dominik

    2014-09-28

    Methanol synthesis from CO and H2 over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partially hydroxylated and defective ZnO(0001¯) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving "near-surface" molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H2 stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive

  16. Methanol synthesis on ZnO(000overline{1}). IV. Reaction mechanisms and electronic structure

    Science.gov (United States)

    Frenzel, Johannes; Marx, Dominik

    2014-09-01

    Methanol synthesis from CO and H2 over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partially hydroxylated and defective ZnO(000overline{1}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving "near-surface" molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H2 stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on

  17. Electron attachment to oxygen, water, and methanol, in various drift chamber gas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Huk, M.; Igo-Kemenes, P.; Wagner, A.

    1988-04-15

    Attachment of electrons to oxygen, water, and methanol molecules has been studied in various gas mixtures based on argon, methane and isobutane, a class of gases often used to operate large drift chambers. The measurements were performed using a drift chamber in which the conditions prevailing in large experiments could be closely reproduced. Attachment coefficients were extracted as a function of the gas composition and pressure, the drift field, and the concentration of the molecules under investigation. The observed effects are compared to other measurements, and are discussed within the frame of physical models. (orig.)

  18. Electron attachment to oxygen, water, and methanol, in various drift chamber gas mixtures

    Science.gov (United States)

    Huk, M.; Igo-Kemenes, P.; Wagner, A.

    1988-04-01

    Attachment of electrons to oxygen, water, and methanol molecules has been studied in various gas mixtures based on argon, methane and isobutane, a class of gases often used to operate large drift chambers. The measurements were performed using a drift chamber in which the conditions prevailing in large experiments could be closely reproduced. Attachment coefficients were extracted as a function of the gas composition and pressure, the drift field, and the concentration of the molecules under investigation. The observed effects are compared to other measurements, and are discussed within the frame of physical models.

  19. Esterification condition of rapeseed oil fatty acid in supercritical methanol%菜籽油脂肪酸在超临界甲醇中酯化反应工艺条件研究

    Institute of Scientific and Technical Information of China (English)

    李一哲; 王华; 包桂蓉; 李法社

    2014-01-01

    以菜籽油在亚临界水解反应中制取的脂肪酸为原料,研究菜籽油脂肪酸在超临界甲醇中的酯化反应工艺条件及动力学模型。通过单因素试验考察了反应温度、醇酸体积比、反应压力、反应时间对酯化转化率的影响,并采用超高效液相色谱法分析油酸甲酯含量的变化情况。试验结果表明菜籽油脂肪酸在超临界甲醇中酯化反应的最佳工艺条件为:反应温度270℃,反应时间40 min,反应压力25 MPa,醇酸体积比2:1。在最佳工艺条件下菜籽油脂肪酸酯化转化率超过了98%,动力学模型为- dCA dt =62.98e-20.14/ RT C1.8A 。%With the fatty acid prepared by hydrolyzing rapeseed oil in subcritical water as raw material, the esterification conditions and kinetics model of rapeseed oil fatty acid in supercritical methanol were studied. The effects of reaction temperature, volume ratio of methanol to rapeseed oil fatty acid, reaction pressure and reaction time on the conversion rate of the esterification were investigated by single factor ex-periment,and the content change of methyl oleate was analyzed by ultra performance liquid chromatogra-phy. The results showed that the optimal esterification conditions of rapeseed oil fatty acid in supercritical methanol were obtained as follows: reaction temperature 270 ℃, reaction time 40 min, reaction pressure 25 MPa and volume ratio of methanol to rapeseed oil fatty acid 2: 1. Under the optimal conditions, the conversion rate of rapeseed oil fatty acid was over 98% and the kinetics model was - dCA 62. 98e - 20 . 14 / RTC1. 8A . dt =62. 98e-20. 14/ RT C1. 8 A .

  20. Antimicrobial Activities of Methanol, Ethanol and Supercritical CO2 Extracts of Philippine Piper betle L. on Clinical Isolates of Gram Positive and Gram Negative Bacteria with Transferable Multiple Drug Resistance.

    Directory of Open Access Journals (Sweden)

    Demetrio L Valle

    Full Text Available Piper betle L. has traditionally been used in alternative medicine in different countries for various therapeutic purposes, including as an anti-infective agent. However, studies reported in the literature are mainly on its activities on drug susceptible bacterial strains. This study determined the antimicrobial activities of its ethanol, methanol, and supercritical CO2 extracts on clinical isolates of multiple drug resistant bacteria which have been identified by the Infectious Disease Society of America as among the currently more challenging strains in clinical management. Assay methods included the standard disc diffusion method and the broth microdilution method for the determination of the minimum inhibitory concentration (MIC and the minimum bactericidal concentrations (MBC of the extracts for the test microorganisms. This study revealed the bactericidal activities of all the P. betle leaf crude extracts on methicillin-resistant Staphylococcus aureus (MRSA, vancomycin-resistant Enterococcus (VRE, extended spectrum β-lactamase-producing Enterobacteriaceae, carbapenem-resistant Enterobacteriaceae, and metallo-β-lactamase-producing Pseudomonas aeruginosa and Acinetobacter baumannii, with minimum bactericidal concentrations that ranged from 19μg/ml to 1250 μg/ml. The extracts proved to be more potent against the Gram positive MRSA and VRE than for the Gram negative test bacteria. VRE isolates were more susceptible to all the extracts than the MRSA isolates. Generally, the ethanol extracts proved to be more potent than the methanol extracts and supercritical CO2 extracts as shown by their lower MICs for both the Gram positive and Gram negative MDRs. MTT cytotoxicity assay showed that the highest concentration (100 μg/ml of P. betle ethanol extract tested was not toxic to normal human dermal fibroblasts (HDFn. Data from the study firmly established P. betle as an alternative source of anti-infectives against multiple drug resistant

  1. Antimicrobial Activities of Methanol, Ethanol and Supercritical CO2 Extracts of Philippine Piper betle L. on Clinical Isolates of Gram Positive and Gram Negative Bacteria with Transferable Multiple Drug Resistance.

    Science.gov (United States)

    Valle, Demetrio L; Cabrera, Esperanza C; Puzon, Juliana Janet M; Rivera, Windell L

    2016-01-01

    Piper betle L. has traditionally been used in alternative medicine in different countries for various therapeutic purposes, including as an anti-infective agent. However, studies reported in the literature are mainly on its activities on drug susceptible bacterial strains. This study determined the antimicrobial activities of its ethanol, methanol, and supercritical CO2 extracts on clinical isolates of multiple drug resistant bacteria which have been identified by the Infectious Disease Society of America as among the currently more challenging strains in clinical management. Assay methods included the standard disc diffusion method and the broth microdilution method for the determination of the minimum inhibitory concentration (MIC) and the minimum bactericidal concentrations (MBC) of the extracts for the test microorganisms. This study revealed the bactericidal activities of all the P. betle leaf crude extracts on methicillin-resistant Staphylococcus aureus (MRSA), vancomycin-resistant Enterococcus (VRE), extended spectrum β-lactamase-producing Enterobacteriaceae, carbapenem-resistant Enterobacteriaceae, and metallo-β-lactamase-producing Pseudomonas aeruginosa and Acinetobacter baumannii, with minimum bactericidal concentrations that ranged from 19μg/ml to 1250 μg/ml. The extracts proved to be more potent against the Gram positive MRSA and VRE than for the Gram negative test bacteria. VRE isolates were more susceptible to all the extracts than the MRSA isolates. Generally, the ethanol extracts proved to be more potent than the methanol extracts and supercritical CO2 extracts as shown by their lower MICs for both the Gram positive and Gram negative MDRs. MTT cytotoxicity assay showed that the highest concentration (100 μg/ml) of P. betle ethanol extract tested was not toxic to normal human dermal fibroblasts (HDFn). Data from the study firmly established P. betle as an alternative source of anti-infectives against multiple drug resistant bacteria.

  2. Methanol fixation of plant tissue for Scanning Electron Microscopy improves preservation of tissue morphology and dimensions.

    Science.gov (United States)

    Talbot, Mark J; White, Rosemary G

    2013-10-02

    It is well known that preparation of biological (plant and animal) tissues for Scanning Electron Microscopy (SEM) by chemical fixation and critical point drying results in shrinkage of tissues, often by up to 20-30%, depending on the tissue type and fixation protocol used. We sought to identify a protocol that would preserve tissue size and morphology better than standard chemical fixatives and dehydration regimes. We compared a range of processing techniques by quantifying changes in tissue size and recording details of surface morphology using leaf tissues from three commonly studied species; Arabidopsis thaliana, barley and cotton. All processing protocols altered tissue dimensions. Methanol fixation and dehydration, followed by a further short (1 h) dehydration step in ethanol and critical point drying (which was based on a previously published method), preserved tissue dimensions most consistently of all protocols tested, although it did cause 8% shrinkage in all three species. This protocol was also best for preservation of surface morphology in all three species. We outline a recommended protocol and advise that the method is best trialled for different tissues, especially thicker or larger samples. This study shows that simultaneous fixation and dehydration in methanol followed by ethanol results in better preservation of dimensions and morphology of critical point dried plant tissues than other fixation and dehydration procedures. It is a quick and simple method, and requires standard SEM preparation equipment.

  3. Investigation of Mineral Transformations in Wet Supercritical CO2 by Electron Microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Arey, Bruce W.; Kovarik, Libor; Wang, Zheming; Felmy, Andrew R.

    2011-10-10

    The capture and storage of carbon dioxide and other greenhouse gases in deep geologic formations represents one of the most promising options for mitigating the impacts of greenhouse gases on global warming. In this regard, mineral-fluid interactions are of prime importance since such reactions can result in the long term sequestration of CO2 by trapping in mineral phases. Recently it has been recognized that interactions with neat to water-saturated non-aqueous fluids are of prime importance in understanding mineralization reactions since the introduced CO2 is likely to contain water initially or soon after injection and the supercritical CO2 (scCO2) is less dense than the aqueous phase which can result in a buoyant scCO2 plume contacting the isolating caprock. As a result, unraveling the molecular/microscopic mechanisms of mineral transformation in neat to water saturated scCO2 has taken on an added important. In this study, we are examining the interfacial reactions of the olivine mineral forsterite (Mg2SiO4) over a range of water contents up to and including complete water saturation in scCO2. The surface precipitates that form on the reacted forsterite grains are extremely fragile and difficult to experimentally characterize. In order to address this issue we have developed experimental protocols for preparing and imaging electron-transparent samples from fragile structures. These electron-transparent samples are then examined using a combination of STEM/EDX, FIB-TEM, and helium ion microscope (HIM) imaging (Figures 1-3). This combination of capabilities has provided unique insight into the geochemical processes that occur on scCO2 reacted mineral surfaces. The experimental procedures and protocols that have been developed also have useful applications for examining fragile structures on a wide variety of materials. This research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and

  4. Supercritical water

    CERN Document Server

    Marcus, Yizhak

    2012-01-01

    Discover the many new and emerging applications of supercritical water as a green solvent Drawing from thousands of original research articles, this book reviews and summarizes what is currently known about the properties and uses of supercritical water. In particular, it focuses on new and emerging applications of supercritical water as a green solvent, including the catalytic conversion of biomass into fuels and the oxidation of hazardous materials. Supercritical Water begins with an introduction that defines supercritical fluids in general. It then defines supercritical wa

  5. Electron Microscopic Analysis and Biochemical Characterization of a Novel Methanol Dehydrogenase from the Thermotolerant Bacillus sp. C1

    NARCIS (Netherlands)

    Vonck, Janet; Arfman, Nico; Vries, Gert E. de; Beeumen, Jozef van; Bruggen, Ernst F.J. van; Dijkhuizen, Lubbert

    1991-01-01

    Methanol dehydrogenase from the thermotolerant Bacillus sp. C1 was studied by electron microscopy and image processing. Two main projections can be distinguished: one exhibits 5-fold symmetry and has a diameter of 15 nm, the other is rectangular with sides of 15 and 9 nm. Subsequent image processing

  6. Supercritical CO2-based solvents in next generation micro- electronics processing

    Institute of Scientific and Technical Information of China (English)

    ZHANG XiaoGang; Keith P.JOHNSTON

    2007-01-01

    Large amount of chemicals and highly purified-water are needed in microelectronic manufacture. The ability of solutions to penetrate tiny spaces will become significantly more challenging as the feature size of semiconductor devices decreases to nanoscale dimensions and the functional complexity of integrated circuitries (ICs) ever increases. Supercritical fluids (SCFs) possess a unique combination of properties (no surface tension and gas-like viscosity) that can potentially be exploited for application in microelectronics manufacturing and processing in response to needs for material-compatible cleaning systems, small-dimension developing solvents, and low chemical-use processes. Recent microelectronics processes for cleaning and rinsing of patterned porous low-k dielectrics and drying of photoresist in CO2-based solvents are the main focus of this review. Additional topics in supercritical fluid processing include spin coating of photoresists, development with nanoscale dimensions, metal deposition and silylation.

  7. Pulsed corona discharge at atmospheric and supercritical conditions

    Science.gov (United States)

    Lock, Evgeniya Hristova

    Pulsed corona discharge is one of the non-equilibrium plasma techniques, by which electrical power is mainly utilized to generate high-energy electrons. These react further with the background gas to produce radicals, which can be further employed in chemically selective reactions. Study of the initiation of pulsed corona discharge in carbon dioxide and air was conducted. Furthermore due to its high removal efficiency, energy yields and good economy, the pulsed corona discharge was employed for removal of methanol and dimethyl sulfide. These compounds are part of the volatile organic compounds (VOC) air pollutants, which are subject of severe environmental regulations due to their toxicity, environmental persistence and intensity of smell. The study provides experimental data for the destruction of methanol and dimethyl sulfide from dry and humid air streams. The effects of the process parameters, including applied voltage, pulse repetition rate, initial concentration of pollutants, temperature and humidity on the destruction and removal efficiency and energy cost are analyzed. Specific consideration is given to the formation of unwanted byproducts. The study on plasma application for pollution control showed that small amounts of dispersed liquid droplets increase the efficiency of the chemical utilization of the high-energy electrons and reduce the required power. So media that could facilitate homogeneous and heterogeneous chemistry at the same time would enhance the efficiency of the removal process. Such medium that has properties intermediate between the gas and liquid phase is the supercritical fluid. Generation of plasma in supercritical fluids is an unexplored area in plasma science. The generation of plasma at elevated pressures usually requires high voltages or small interelectrode distances. The supercritical phase is characterized by extensive cluster formation in the vicinity of the critical point. Typically the clusters have lower ionization

  8. Constraints on changes in the proton-electron mass ratio using methanol lines

    CERN Document Server

    Kanekar, N; Menten, K M; Bagdonaite, J; Brunthaler, A; Henkel, C; Muller, S; Bethlem, H L; Dapra, M

    2014-01-01

    We report Karl G. Jansky Very Large Array (VLA) absorption spectroscopy in four methanol (CH$_3$OH) lines in the $z = 0.88582$ gravitational lens towards PKS1830-211. Three of the four lines have very different sensitivity coefficients $K_\\mu$ to changes in the proton-electron mass ratio $\\mu$; a comparison between the line redshifts thus allows us to test for temporal evolution in $\\mu$. We obtain a stringent statistical constraint on changes in $\\mu$ by comparing the redshifted 12.179 GHz and 60.531 GHz lines, $[\\Delta mu/\\mu] \\leq 1.1 \\times 10^{-7}$ ($2\\sigma$) over $0 4\\sigma$ significance). The sensitivity of the above result, and that of all earlier CH$_3$OH studies, is thus likely to be limited by unknown systematic errors, probably arising due to the frequency-dependent structure of PKS1830-211. A robust result is obtained by combining the three lines at similar frequencies, 48.372, 48.377 and 60.531 GHz, whose line profiles are found to be in good agreement. This yields the $2\\sigma$ constraint $[\\...

  9. Electronic and vibrational spectroscopy of intermediates in methane-to-methanol conversion by CoO+

    Science.gov (United States)

    Altinay, Gokhan; Kocak, Abdulkadir; Silva Daluz, Jennifer; Metz, Ricardo B.

    2011-08-01

    At room temperature, cobalt oxide cations directly convert methane to methanol with high selectivity but very low efficiency. Two potential intermediates of this reaction, the [HO-Co-CH3]+ insertion intermediate and [H2O-Co=CH2]+ aquo-carbene complex are produced in a laser ablation source and characterized by electronic and vibrational spectroscopy. Reaction of laser-ablated cobalt cations with different organic precursors seeded in a carrier gas produces the intermediates, which subsequently expand into vacuum and cool. Ions are extracted into a time-of-flight mass spectrometer and spectra are measured via photofragment spectroscopy. Photodissociation of [HO-Co-CH3]+ in the visible and via infrared multiple photon dissociation (IRMPD) makes only Co+ + CH3OH, while photodissociation of [H2O-Co=CH2]+ produces CoCH2+ + H2O. The electronic spectrum of [HO-Co-CH3]+ shows progressions in the excited state Co-C stretch (335 cm-1) and O-Co-C bend (90 cm-1); the IRMPD spectrum gives νOH = 3630 cm-1. The [HO-Co-CH3]+(Ar) complex has been synthesized and its vibrational spectrum measured in the O-H stretching region. The resulting spectrum is sharper than that obtained via IRMPD and gives νOH = 3642 cm-1. Also, an improved potential energy surface for the reaction of CoO+ with methane has been developed using single point energies calculated by the CBS-QB3 method for reactants, intermediates, transition states and products.

  10. Supercritical multicomponent solvent coal extraction

    Science.gov (United States)

    Corcoran, W. H.; Fong, W. S.; Pichaichanarong, P.; Chan, P. C. F.; Lawson, D. D. (Inventor)

    1983-01-01

    The yield of organic extract from the supercritical extraction of coal with larger diameter organic solvents such as toluene is increased by use of a minor amount of from 0.1 to 10% by weight of a second solvent such as methanol having a molecular diameter significantly smaller than the average pore diameter of the coal.

  11. Electronic modification of Pt via Ti and Se as tolerant cathodes in air-breathing methanol microfluidic fuel cells.

    Science.gov (United States)

    Ma, Jiwei; Habrioux, Aurélien; Morais, Cláudia; Alonso-Vante, Nicolas

    2014-07-21

    We reported herein on the use of tolerant cathode catalysts such as carbon supported Pt(x)Ti(y) and/or Pt(x)Se(y) nanomaterials in an air-breathing methanol microfluidic fuel cell. In order to show the improvement of mixed-reactant fuel cell (MRFC) performances obtained with the developed tolerant catalysts, a classical Pt/C nanomaterial was used for comparison. Using 5 M methanol concentration in a situation where the fuel crossover is 100% (MRFC-mixed reactant fuel cell application), the maximum power density of the fuel cell with a Pt/C cathodic catalyst decreased by 80% in comparison with what is observed in the laminar flow fuel cell (LFFC) configuration. With Pt(x)Ti(y)/C and Pt(x)Se(y)/C cathode nanomaterials, the performance loss was only 55% and 20%, respectively. The evaluation of the tolerant cathode catalysts in an air-breathing microfluidic fuel cell suggests the development of a novel nanometric system that will not be size restricted. These interesting results are the consequence of the high methanol tolerance of these advanced electrocatalysts via surface electronic modification of Pt. Herein we used X-ray photoelectron and in situ FTIR spectroscopies to investigate the origin of the high methanol tolerance on modified Pt catalysts.

  12. Degradation Characteristics of Wood Using Supercritical Alcohols

    Directory of Open Access Journals (Sweden)

    Jeeban Poudel

    2012-11-01

    Full Text Available In this work, the characteristics of wood degradation using supercritical alcohols have been studied. Supercritical ethanol and supercritical methanol were used as solvents. The kinetics of wood degradation were analyzed using the nonisothermal weight loss technique with heating rates of 3.1, 9.8, and 14.5 °C/min for ethanol and 5.2, 11.3, and 16.3 °C/min for methanol. Three different kinetic analysis methods were implemented to obtain the apparent activation energy and the overall reaction order for wood degradation using supercritical alcohols. These were used to compare with previous data for supercritical methanol. From this work, the activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol for the different kinetic analysis methods used in this work. The activation energies of wood degradation in supercritical ethanol were obtained as 78.0–86.0, 40.1–48.1, and 114 kJ/mol. This paper also includes the analysis of the liquid products obtained from this work. The characteristic analysis of liquid products on increasing reaction temperature and time has been performed by GC-MS. The liquid products were categorized according to carbon numbers and aromatic/aliphatic components. It was found that higher conversion in supercritical ethanol occurs at a lower temperature than that of supercritical methanol. The product analysis shows that the majority of products fall in the 2 to 15 carbon number range.

  13. Investigation of water and methanol sorption in monovalent- and multivalent-ion-exchanged nafion membranes using electron spin resonance.

    Science.gov (United States)

    Lawton, Jamie S; Budil, David E

    2009-08-06

    Electron spin resonance (ESR) spectroscopy was used to monitor the local environment of 2,2,6,6-tetramethyl-4-piperidone N-oxide (TEMPONE) spin probe in Li(+), Ca(2+), and Al(3+) ion-exchanged Nafion 117 membranes swollen with mixed methanol/water solvent at varying compositions. The (14)N hyperfine splitting, a(N), which reflects the local polarity of the nitroxide probe, remains nearly steady at higher solvent contents but increases substantially at lower solvent contents, reflecting close contact with the ions. The rotational rate (R) of the probe increased with solvent content, depending strongly on the amount of solvent at low contents but increasing more gradually at higher solvent contents, similar to the behavior of previously measured solvent translation diffusion coefficients. The rotational rate data from water-containing membranes were fitted using the Fujita free-volume diffusion model, which indicated that multivalent ions tend to increase the free volume fraction of the polymer while decreasing that of the solvent phase. Methanol-containing membranes exhibited greater variation with different exchange ions, but the data could not be fit using the free-volume model, suggesting that the assumption of two phases underlying the free-volume model might not apply to this case. The difference in the trends of swelling between water and methanol is consistent with previous results that have indicated different patterns of penetration for the two solvents. The results are interpreted in terms of changes in membrane morphology with higher-valence ions.

  14. First cosmological constraints on the proton-to-electron mass ratio from observations of rotational transitions of methanol

    CERN Document Server

    Ellingsen, S P; Breen, S L; Lovell, J E J

    2012-01-01

    We have used the Australia Telescope Compact Array to measure the absorption from the 2(0) - 3(-1}E 12.2 GHz transition of methanol towards the z=0.89 lensing galaxy in the PKS B 1830-211 gravitational lens system. Comparison of the velocity of the main absorption feature with the published absorption spectrum from the 1(0) - 2(-1)E transition of methanol shows that they differ by -0.6 +/- 1.6 km/s . We can use these observations to constrain the changes in the proton-to-electron mass ratio from z=0.89 to the present to 0.8 +/- 2.1 x 10^-7. This result is consistent, and of similar precision to recent observations at z = 0.68 achieved through comparison of a variety of rotational and inversion transitions, and approximately a factor of 2 better than previous constraints obtained in this source. Future more sensitive observations which incorporate additional rotational methanol transitions offer the prospect of improving current results by a factor of 5-10.

  15. Electrochemical Reduction of Carbon Dioxide to Methanol by Direct Injection of Electrons into Immobilized Enzymes on a Modified Electrode.

    Science.gov (United States)

    Schlager, Stefanie; Dumitru, Liviu Mihai; Haberbauer, Marianne; Fuchsbauer, Anita; Neugebauer, Helmut; Hiemetsberger, Daniela; Wagner, Annika; Portenkirchner, Engelbert; Sariciftci, Niyazi Serdar

    2016-03-21

    We present results for direct bio-electrocatalytic reduction of CO2 to C1 products using electrodes with immobilized enzymes. Enzymatic reduction reactions are well known from biological systems where CO2 is selectively reduced to formate, formaldehyde, or methanol at room temperature and ambient pressure. In the past, the use of such enzymatic reductions for CO2 was limited due to the necessity of a sacrificial co-enzyme, such as nicotinamide adenine dinucleotide (NADH), to supply electrons and the hydrogen equivalent. The method reported here in this paper operates without the co-enzyme NADH by directly injecting electrons from electrodes into immobilized enzymes. We demonstrate the immobilization of formate, formaldehyde, and alcohol dehydrogenases on one-and-the-same electrode for direct CO2 reduction. Carbon felt is used as working electrode material. An alginate-silicate hybrid gel matrix is used for the immobilization of the enzymes on the electrode. Generation of methanol is observed for the six-electron reduction with Faradaic efficiencies of around 10%. This method of immobilization of enzymes on electrodes offers the opportunity for electrochemical application of enzymatic electrodes to many reactions in which a substitution of the expensive sacrificial co-enzyme NADH is desired.

  16. Corrosion in supercritical fluids

    Energy Technology Data Exchange (ETDEWEB)

    Propp, W.A.; Carleson, T.E.; Wai, Chen M.; Taylor, P.R.; Daehling, K.W.; Huang, Shaoping; Abdel-Latif, M.

    1996-05-01

    Integrated studies were carried out in the areas of corrosion, thermodynamic modeling, and electrochemistry under pressure and temperature conditions appropriate for potential applications of supercritical fluid (SCF) extractive metallurgy. Carbon dioxide and water were the primary fluids studied. Modifiers were used in some tests; these consisted of 1 wt% water and 10 wt% methanol for carbon dioxide and of sulfuric acid, sodium sulfate, ammonium sulfate, and ammonium nitrate at concentrations ranging from 0.00517 to 0.010 M for the aqueous fluids. The materials studied were Types 304 and 316 (UNS S30400 and S31600) stainless steel, iron, and AISI-SAE 1080 (UNS G10800) carbon steel. The thermodynamic modeling consisted of development of a personal computer-based program for generating Pourbaix diagrams at supercritical conditions in aqueous systems. As part of the model, a general method for extrapolating entropies and related thermodynamic properties from ambient to SCF conditions was developed. The experimental work was used as a tool to evaluate the predictions of the model for these systems. The model predicted a general loss of passivation in iron-based alloys at SCF conditions that was consistent with experimentally measured corrosion rates and open circuit potentials. For carbon-dioxide-based SCFs, measured corrosion rates were low, indicating that carbon steel would be suitable for use with unmodified carbon dioxide, while Type 304 stainless steel would be suitable for use with water or methanol as modifiers.

  17. Supercritical Fluid Facilitated Growth of Copper and Aluminum Oxide Nanoparticles

    Science.gov (United States)

    Williams, Geoffrey L.; Vohs, Jason K.; Brege, Jonathan J.; Fahlman, Bradley D.

    2005-01-01

    Supercritical fluids (SCFs) possess properties that are intermediate between liquids and gases. The combination of supercritical fluid technology with advanced characterization techniques such as electron microscopy provided a practical and rewarding undergraduate laboratory experiment.

  18. 生物油中反应性化合物对羧酸在超临界甲醇中酯化的影响%Effect of the reactive compounds in bio-oils on esterification of the contained carboxylic acids in supercritical methanol

    Institute of Scientific and Technical Information of China (English)

    崔洪友; 马成亮; 李志合; 易维明

    2011-01-01

    采用乙酸(AC)、丙烯酸(AR)、乙酰丙酮(AA)、糠醛、2-甲氧基苯酚(MP)和水等组分,研究了羧酸在超临界甲醇中的酯化反应,并考察了各种组分对酯化反应的影响.通过两种羧酸单独酯化和共同酯化的特性以及水分影响的考察发现,超临界酯化过程中存在着不同酸的酯交换作用;水分对酯化反应具有明显的抑制作用,但超临界酯化时具有更高的耐水性.水分的抑制作用主要是削弱了羰基正离子的亲电能力,降低酯化反应速率,而不是因为化学反应平衡移动.超临界酯化的高温可加快反应速率,较弱的氢键环境可部分抵消羰基正离子亲电能力的削弱作用.AA和糠醛对酯化反应基本没有影响,但AA自身会被转化为丙酮和乙酸甲酯,而糠醛会发生缩醛化反应.MP对AR的酯化具有促进作用,并抑制聚合,从而可以提高酯化的转化率和选择性.%Using acetic acid ( AC ), acrylic acid (AR), acetyl acetone (AA), furfural, 2-methoxy phenol (MP) and water as representative compounds and p-toluene sulfonic acid as catalyst, the esterification upgrading was examined in supercritical methanol and under atmosphere pressure. The comparison results of esterification and simultaneous esterification of AC and AR as well as the effect of water show that supercritical esterification is superior to normal liquid-phase esterification in view of acid removal. Furthermore, transesterification reaction could take place when simultaneously esterifying mixed acids in supercritical methanol, leading to relatively higher conversion for the acid like AR which hardly reacts with methanol at normal condition. The reason for low acid conversion in the presence of water is attributed to the retarding effect of water on esterification, rather than a result of equilibrium shifting, since water tends to weaken the electrophilicity of positive carbonyl ion. However, such effect in supercritical methanol is much

  19. Pulse electron paramagnetic resonance studies of the interaction of methanol with the S2 state of the Mn4O5Ca cluster of photosystem II.

    Science.gov (United States)

    Oyala, Paul H; Stich, Troy A; Stull, Jamie A; Yu, Fangting; Pecoraro, Vincent L; Britt, R David

    2014-12-23

    The binding of the substrate analogue methanol to the catalytic Mn4CaO5 cluster of the water-oxidizing enzyme photosystem II is known to alter the electronic structure properties of the oxygen-evolving complex without retarding O2-evolution under steady-state illumination conditions. We report the binding mode of (13)C-labeled methanol determined using 9.4 GHz (X-band) hyperfine sublevel-correlation (HYSCORE) and 34 GHz (Q-band) electron spin-echo electron nuclear double resonance (ESE-ENDOR) spectroscopies. These results are compared to analogous experiments on a mixed-valence Mn(III)Mn(IV) complex (2-OH-3,5-Cl2-salpn)2Mn(III)Mn(IV) (salpn = N,N'-bis(3,5-dichlorosalicylidene)-1,3-diamino-2-hydroxypropane) in which methanol ligates to the Mn(III) ion ( Larson et al. (1992) J. Am. Chem. Soc. , 114 , 6263 ). In the mixed-valence Mn(III,IV) complex, the hyperfine coupling to the (13)C of the bound methanol (Aiso = 0.65 MHz, T = 1.25 MHz) is appreciably larger than that observed for (13)C methanol associated with the Mn4CaO5 cluster poised in the S2 state, where only a weak dipolar hyperfine interaction (Aiso = 0.05 MHz, T = 0.27 MHz) is observed. An evaluation of the (13)C hyperfine interaction using the X-ray structure coordinates of the Mn4CaO5 cluster indicates that methanol does not bind as a terminal ligand to any of the manganese ions in the oxygen-evolving complex. We favor methanol binding in place of a water ligand to the Ca(2+) in the Mn4CaO5 cluster or in place of one of the waters that form hydrogen bonds with the oxygen bridges of the cluster.

  20. Measurement of polychlorinated biphenyls in solid waste such as transformer insulation paper by supercritical fluid extraction and gas chromatography electron capture detection.

    Science.gov (United States)

    Chikushi, Hiroaki; Fujii, Yuka; Toda, Kei

    2012-09-21

    In this work, a method for measuring polychlorinated biphenyls (PCBs) in contaminated solid waste was investigated. This waste includes paper that is used in electric transformers to insulate electric components. The PCBs in paper sample were extracted by supercritical fluid extraction and analyzed by gas chromatography-electron capture detection. The recoveries with this method (84-101%) were much higher than those with conventional water extraction (0.08-14%), and were comparable to those with conventional organic solvent extraction. Limit of detection was 0.0074 mg kg(-1) and measurable up to 2.5 mg kg(-1) for 0.5 g of paper sample. Data for real insulation paper by the proposed method agreed well with those by the conventional organic solvent extraction. Extraction from wood and concrete was also investigated and good performance was obtained as well as for paper samples. The supercritical fluid extraction is simpler, faster, and greener than conventional organic solvent extraction. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Density dependence of the yield of hydrated electrons in the low-LET radiolysis of supercritical water at 400 °C: influence of the geminate recombination of subexcitation-energy electrons prior to thermalization.

    Science.gov (United States)

    Meesungnoen, Jintana; Sanguanmith, Sunuchakan; Jay-Gerin, Jean-Paul

    2013-10-21

    Monte Carlo simulations were used to calculate the yield of hydrated electrons (eaq(-)) in the low-linear energy transfer radiolysis of supercritical water at 400 °C as a function of water density over the range of ~0.15 to 0.6 g cm(-3). Very good agreement was found between our calculations and picosecond pulse radiolysis experimental data at ~60 ps and 1 ns at high density (>0.35 g cm(-3)). At densities lower than ~0.35 g cm(-3), our eaq(-) yields were lower than the experimental data, especially at ~60 ps. However, if we incorporated into the simulations a prompt geminate electron-cation (H2O˙(+)) recombination (prior thermalization of the electron) that decreased as the density decreased, our computed eaq(-) yields at ~60 ps and 1 ns compared fairly well with the experimental data for the entire density range studied.

  2. Probing Lewis Acid-Base Interactions with Born-Oppenheimer Molecular Dynamics: The Electronic Absorption Spectrum of p-Nitroaniline in Supercritical CO2.

    Science.gov (United States)

    Cabral, Benedito J Costa; Rivelino, Roberto; Coutinho, Kaline; Canuto, Sylvio

    2015-07-02

    The structure and dynamics of p-nitroaniline (PNA) in supercritical CO2 (scCO2) at T = 315 K and ρ = 0.81 g cm(-3) are investigated by carrying out Born-Oppenheimer molecular dynamics, and the electronic absorption spectrum in scCO2 is determined by time dependent density functional theory. The structure of the PNA-scCO2 solution illustrates the role played by Lewis acid-base (LA-LB) interactions. In comparison with isolated PNA, the ν(N-O) symmetric and asymmetric stretching modes of PNA in scCO2 are red-shifted by -17 and -29 cm(-1), respectively. The maximum of the charge transfer (CT) absorption band of PNA in scSCO2 is at 3.9 eV, and the predicted red-shift of the π → π* electronic transition relative to the isolated gas-phase PNA molecule reproduces the experimental value of -0.35 eV. An analysis of the relationship between geometry distortions and excitation energies of PNA in scCO2 shows that the π → π* CT transition is very sensitive to changes of the N-O bond distance, strongly indicating a correlation between vibrational and electronic solvatochromism driven by LA-LB interactions. Despite the importance of LA-LB interactions to explain the solvation of PNA in scCO2, the red-shift of the CT band is mainly determined by electrostatic interactions.

  3. Supercritical fluid extraction of mercury species.

    Science.gov (United States)

    Foy, G P; Pacey, G E

    2003-12-23

    Supercritical fluid extraction was used to recover organic and inorganic mercury species. Variations in pressure, water, methanol, and chelator create methods that allowed separation of inorganic from organic mercury species. When extracted using a compromised set of extraction conditions, the order of extraction was methyl, phenyl and inorganic mercury. For the individually optimized conditions, quantitative recoveries were observed. Level as low as 20 ppb were extracted and then determined using ICP.

  4. Methanolysis of Poly(ethylene terephthalate) in Supercritical Phase

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The depolymerization of poly(ethylene terephthalate, PET) in supercritical methanol is studied using a stainless stirred autoclave at temperature of 255~260℃, pressure of 8.5~14.0 MPa, and methanol/PET weight ratio of 3~8. Under the optimal conditions, the PET is depolymerized completely to its monomers in 60 min. The main products of the reaction are dimethyl terephthalate and ethylene glycol. There are still some small amounts of byproducts, such as methyl-(2-hydroxyethyl) terephthalate, bis(hydroxyethyl) terephthalate, dimers and oligomers. Reversed-phase high performance liquid chrom- atography and gas chromatography are used to analyze solid products and liquid products respectively. The results of depolymerization show that the yield of dimethyl terephthalate and the degree of PET depolymerization are dependent on the reaction temperature, weight ratio of methanol to PET and reaction time. But the reaction pressure has little influence on the depolymerization as long as methanol is in supercritical state.

  5. Functional separation of oxidation–reduction reactions and electron transport in PtRu/ND and conductive additive hybrid electrocatalysts during methanol oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yan; Wang, Yanhui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Bian, Linyan [College of Physics and Chemistry, Henan Polytechnic University, Jiaozuo, Henan 454000 (China); Lu, Rui [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China); Zang, Jianbing, E-mail: jbzang@ysu.edu.cn [State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004 (China)

    2016-02-28

    Graphical abstract: - Highlights: • Functional separation of reactions and electron transport in PtRu/ND + AB (or CNT). • A conductive network was formed after the addition of AB or CNT. • PtRu/ND + AB (or CNT) exhibited enhanced activity and stability than PtRu/ND. - Abstract: Undoped nanodiamond (ND) supported PtRu (PtRu/ND) electrocatalyst for methanol oxidation reactions (MOR) in direct methanol fuel cells was prepared by a microwave-assisted polyol reduction method. Sp{sup 3}-bonded ND possesses high electrochemical stability but low conductivity, while sp{sup 2}-bonded carbon nanomaterials with high conductivity are prone to oxidation. Therefore, the functions of the supporting material were separated in this study. ND (sp{sup 3}), as a support, and AB or CNTs (sp{sup 2}), as a conductive additive, were combined to form the hybrid electrocatalysts PtRu/ND + AB and PtRu/ND + CNT for MOR. The morphology of the electrocatalysts was characterized by scanning electron microscopy and electrochemical measurements were performed using an electrochemical workstation. The results indicated that the electrocatalytic activity of PtRu/ND for MOR was improved with the addition of AB or CNTs as a conductive additive. Moreover, adding CNTs to PtRu/ND as a conductive additive showed better electrocatalytic activities than adding AB, which can be ascribed to the better electron-transfer ability of CNTs.

  6. Integration of Artificial Photosynthesis System for Enhanced Electronic Energy-Transfer Efficacy: A Case Study for Solar-Energy Driven Bioconversion of Carbon Dioxide to Methanol.

    Science.gov (United States)

    Ji, Xiaoyuan; Su, Zhiguo; Wang, Ping; Ma, Guanghui; Zhang, Songping

    2016-09-01

    Biocatalyzed artificial photosynthesis systems provide a promising strategy to store solar energy in a great variety of chemicals. However, the lack of direct interface between the light-capturing components and the oxidoreductase generally hinders the trafficking of the chemicals and photo-excited electrons into the active center of the redox biocatalysts. To address this problem, a completely integrated artificial photosynthesis system for enhanced electronic energy-transfer efficacy is reported by combining co-axial electrospinning/electrospray and layer-by-layer (LbL) self-assembly. The biocatalysis part including multiple oxidoreductases and coenzymes NAD(H) was in situ encapsulated inside the lumen polyelectrolyte-doped hollow nanofibers or microcapsules fabricated via co-axial electrospinning/electrospray; while the precise and spatial arrangement of the photocatalysis part, including electron mediator and photosensitizer for photo-regeneration of the coenzyme, was achieved by ion-exchange interaction-driven LbL self-assembly. The feasibility and advantages of this integrated artificial photosynthesis system is fully demonstrated by the catalyzed cascade reduction of CO2 to methanol by three dehydrogenases (formate, formaldehyde, and alcohol dehydrogenases), incorporating the photo-regeneration of NADH under visible-light irradiation. Compared to solution-based systems, the methanol yield increases from 35.6% to 90.6% using the integrated artificial photosynthesis. This work provides a novel platform for the efficient and sustained production of a broad range of chemicals and fuels from sunlight.

  7. Supercritical CO2 generation of nanometric structure from Ocimum basilicum mucilage prepared for pharmaceutical applications.

    Science.gov (United States)

    Akbari, Iman; Ghoreishi, Seyyed M; Habibi, Neda

    2015-04-01

    Plant-derived polymers are widely used in the pharmaceutical industry due to their emollient, lack of toxicity, and irritating nature and low cost. In this work, basil seed mucilage was dried using supercritical carbon dioxide phase inversion technique to form a nanometric structure. The obtained polymeric structures were characterized by scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) method, and Fourier transform infrared spectroscopy (FTIR) and compared with the oven-derived sample group. It was demonstrated that the product morphology could be controlled by altering the composition of methanol which functioned as the co-solvent in the nonsolvent stream. The most homogeneous product (60-nm mean pore size diameter, 78 m(2)/g BET surface area with no agglomeration) was obtained with 2.5% methanol. The FTIR data showed that the presence of hydroxyl and carboxyl groups suggested the bioadhesive property of basil seed mucilage was good and many active pharmaceutical compounds might be loaded to the resultant nanometric structure to enhance drug release. Furthermore, the FTIR analyses indicated that the nature of the final product did not change during the supercritical drying procedure.

  8. Stability of wheat germ oil obtained by supercritical carbon dioxide ...

    African Journals Online (AJOL)

    심정은

    with 1,3-regiospecific lipase at different temperatures (40 to 70°C) to produce diglycerides and ... Key words: Supercritical carbon dioxide, wheat germ oil, ethanolysis, .... Methanol (1 mL), replacing the extract, was used as the blank. The.

  9. Direct synthesis of dimethyl carbonate and propylene glycol using potassium bicarbonate as catalyst in supercritical CO2

    National Research Council Canada - National Science Library

    Yicun Wen; Rui Zhang; Yu Cang; Jianchao Zhang; Lixiao Liu; Xuhong Guo; Bin Fan

    2015-01-01

    The improved one-pot synthesis of dimethyl carbonate and propylene glycol from propylene oxide, supercritical carbon dioxide, and methanol with potassium bicarbonate as the catalyst has been reported in this paper...

  10. Simultaneous Graphite Exfoliation and N Doping in Supercritical Ammonia.

    Science.gov (United States)

    Sasikala, Suchithra Padmajan; Huang, Kai; Giroire, Baptiste; Prabhakaran, Prem; Henry, Lucile; Penicaud, Alain; Poulin, Philippe; Aymonier, Cyril

    2016-11-16

    We report the exfoliation of graphite and simultaneous N doping of graphene by two methods: supercritical ammonia treatment and liquid-phase exfoliation with NH4OH. While the supercritical ammonia allowed N doping at a level of 6.4 atom % in 2 h, the liquid-phase exfoliation with NH4OH allowed N doping at a level of 2.7 atom % in 6 h. The N doped graphene obtained via the supercritical ammonia route had few layers (supercritical ammonia as an exfoliation agent and N doping precursor for graphene. Notably, the N doped graphene showed electrocatalytic activity toward oxygen reduction reaction with high durability and good methanol tolerance compared to those of commercial Pt/C catalyst.

  11. 从超临界二氧化碳和甲醇直接合成碳酸二甲酯%DIRECT SYNTHESIS OF DIMETHYL CARBONATE FROM SUPERCRITICAL CARBON DIOXIDE AND METHANOL

    Institute of Scientific and Technical Information of China (English)

    赵天生; 韩怡卓; 孙予罕; 杨彩虹; 李文彬

    1999-01-01

    @@ Dimethyl carbonate (DMC), an environmentally benign intermediate for organic synthesis, has been mainly synthesized through non-phosgene route of oxidative carbonylation[1]. Direct synthesis of DMC from carbon dioxide and methanol is of more significance due to atom economy. Organometallic compounds of formulae R2M(OR)2, M(OR)2 or M(OR)4[2,3] were employed as catalysts in direct synthesis of DMC, where an activation mechanism of CO2 insertion into metal-oxygen bond was supposed. Unfortunately, the yield of DMC was low even in the presence of chemical dehydrants because mainly of thermodynamic limit.

  12. Supercritical CO{sub 2} fluid for chip resistor cleaning

    Energy Technology Data Exchange (ETDEWEB)

    Wang, C.W.; Chang, R.T.; Lin, W.K.; Lin, R.D.; Liang, M.T.; Yang, J.F.; Wang, J.B.

    1999-09-01

    The cleaning ability of supercritical CO{sub 2} was examined on chip resistors. Extraction analyses were made by atomic absorption spectroscopy and the extent of surface cleaning observed by scanning electron microscopy. Experimental results showed that the flow-cleaning process of supercritical CO{sub 2} possessed the advantages of having a superior cleaning ability and permitting a nondrying step. These characteristics strongly suggest that supercritical CO{sub 2} is a superior alternative to the traditional deionized water used in rinsing chip resistors. Moreover, a higher pressure and temperature can benefit the cleaning ability of this novel supercritical CO{sub 2} cleaning technique.

  13. Diiodination of Alkynes in supercritical Carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 谢叶香; 尹笃林; 江焕峰

    2003-01-01

    A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃.

  14. Quantum mechanics capacitance molecular mechanics modeling of core-electron binding energies of methanol and methyl nitrite on Ag(111) surface

    Science.gov (United States)

    Löytynoja, T.; Li, X.; Jänkälä, K.; Rinkevicius, Z.; Ågren, H.

    2016-07-01

    We study a newly devised quantum mechanics capacitance molecular mechanics (QMCMM) method for the calculation of core-electron binding energies in the case of molecules adsorbed on metal surfaces. This yet untested methodology is applied to systems with monolayer of methanol/methyl nitrite on an Ag(111) surface at 100 K temperature. It was found out that the studied C, N, and O 1s core-hole energies converge very slowly as a function of the radius of the metallic cluster, which was ascribed to build up of positive charge on the edge of the Ag slab. Further analysis revealed that an extrapolation process can be used to obtain binding energies that deviated less than 0.5 eV against experiments, except in the case of methanol O 1s where the difference was as large as 1.8 eV. Additional QM-cluster calculations suggest that the latter error can be connected to the lack of charge transfer over the QM-CMM boundary. Thus, the results indicate that the QMCMM and QM-cluster methods can complement each other in a holistic picture of molecule-adsorbate core-ionization studies, where all types of intermolecular interactions are considered.

  15. Electron-stimulated reactions in layered CO/H{sub 2}O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Petrik, Nikolay G.; Kimmel, Greg A., E-mail: gregory.kimmel@pnnl.gov [Physical Sciences Division, Pacific Northwest National Laboratory, MSIN K8-88, P.O. Box 999, Richland, Washington 99352 (United States); Monckton, Rhiannon J.; Koehler, Sven P. K. [School of Chemistry, The University of Manchester, Manchester M13 9PL (United Kingdom); Photon Science Institute, The University of Manchester, Manchester M13 9PL (United Kingdom); UK Dalton Cumbrian Facility, The University of Manchester, Moor Row, Whitehaven CA24 3HA (United Kingdom)

    2014-05-28

    Low-energy (100 eV) electron-stimulated reactions in layered H{sub 2}O/CO/H{sub 2}O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H{sub 2}O and D{sub 2}O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10–50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations.

  16. Quantum mechanics capacitance molecular mechanics modeling of core-electron binding energies of methanol and methyl nitrite on Ag(111) surface.

    Science.gov (United States)

    Löytynoja, T; Li, X; Jänkälä, K; Rinkevicius, Z; Ågren, H

    2016-07-14

    We study a newly devised quantum mechanics capacitance molecular mechanics (QMCMM) method for the calculation of core-electron binding energies in the case of molecules adsorbed on metal surfaces. This yet untested methodology is applied to systems with monolayer of methanol/methyl nitrite on an Ag(111) surface at 100 K temperature. It was found out that the studied C, N, and O 1s core-hole energies converge very slowly as a function of the radius of the metallic cluster, which was ascribed to build up of positive charge on the edge of the Ag slab. Further analysis revealed that an extrapolation process can be used to obtain binding energies that deviated less than 0.5 eV against experiments, except in the case of methanol O 1s where the difference was as large as 1.8 eV. Additional QM-cluster calculations suggest that the latter error can be connected to the lack of charge transfer over the QM-CMM boundary. Thus, the results indicate that the QMCMM and QM-cluster methods can complement each other in a holistic picture of molecule-adsorbate core-ionization studies, where all types of intermolecular interactions are considered.

  17. Supercritical fluid extraction

    Science.gov (United States)

    Wai, Chien M.; Laintz, Kenneth

    1994-01-01

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

  18. Synthesis of biodiesel from edible and non-edible oils in supercritical alcohols and enzymatic synthesis in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Vivek Rathore; Giridhar Madras [Indian Institute of Science, Bangalore (India). Department of Chemical Engineering

    2007-12-15

    Biodiesel is an attractive alternative fuel because it is environmentally friendly and can be synthesized from edible and non-edible oils. The synthesis of biodiesel from edible oils like palm oil and groundnut oil and from crude non-edible oils like Pongamia pinnata and Jatropha curcas was investigated in supercritical methanol and ethanol without using any catalyst from 200 to 400{sup o}C at 200 bar. The variables affecting the conversion during transesterification, such as molar ratio of alcohol to oil, temperature and time were investigated in supercritical methanol and ethanol. Biodiesel was also synthesized enzymatically with Novozym-435 lipase in presence of supercritical carbon dioxide. The effect of reaction variables such as temperature, molar ratio, enzyme loading and kinetics of the reaction was investigated for enzymatic synthesis in supercritical carbon dioxide. Very high conversions (>80%) were obtained within 10 min and nearly complete conversions were obtained at within 40 min for the synthesis of biodiesel in supercritical alcohols. However, conversions of only 60-70% were obtained in the enzymatic synthesis even after 8 h. 48 refs., 8 figs., 1 tab.

  19. Method for making methanol

    Science.gov (United States)

    Mednick, R. Lawrence; Blum, David B.

    1986-01-01

    Methanol is made in a liquid-phase methanol reactor by entraining a methanol-forming catalyst in an inert liquid and contacting said entrained catalyst with a synthesis gas comprising hydrogen and carbon monoxide.

  20. Effect of supercritical fluid density on nanoencapsulated drug particle size using the supercritical antisolvent method.

    Science.gov (United States)

    Kalani, Mahshid; Yunus, Robiah

    2012-01-01

    The reported work demonstrates and discusses the effect of supercritical fluid density (pressure and temperature of supercritical fluid carbon dioxide) on particle size and distribution using the supercritical antisolvent (SAS) method in the purpose of drug encapsulation. In this study, paracetamol was encapsulated inside L-polylactic acid, a semicrystalline polymer, with different process parameters, including pressure and temperature, using the SAS process. The morphology and particle size of the prepared nanoparticles were determined by scanning electron microscopy and transmission electron microscopy. The results revealed that increasing temperature enhanced mean particle size due to the plasticizing effect. Furthermore, increasing pressure enhanced molecular interaction and solubility; thus, particle size was reduced. Transmission electron microscopy images defined the internal structure of nanoparticles. Thermal characteristics of nanoparticles were also investigated via differential scanning calorimetry. Furthermore, X-ray diffraction pattern revealed the changes in crystallinity structure during the SAS process. In vitro drug release analysis determined the sustained release of paracetamol in over 4 weeks.

  1. Effect of supercritical carbon dioxide on the enzymatic production of biodiesel from waste animal fat using immobilized Candida antarctica lipase B variant

    National Research Council Canada - National Science Library

    Pollardo, Aldricho Alpha; Lee, Hong-shik; Lee, Dohoon; Kim, Sangyong; Kim, Jaehoon

    2017-01-01

    .... However, enzymatic reaction still has some drawbacks such as lower reaction rates than base-catalyzed transesterification and the limitation of reactant concentration due to the enzyme inhibition of methanol. Supercritical CO.sub...

  2. Electrochemistry in supercritical fluids

    Science.gov (United States)

    Branch, Jack A.; Bartlett, Philip N.

    2015-01-01

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide–acetonitrile and supercritical HFCs. PMID:26574527

  3. Electrochemistry in supercritical fluids.

    Science.gov (United States)

    Branch, Jack A; Bartlett, Philip N

    2015-12-28

    A wide range of supercritical fluids (SCFs) have been studied as solvents for electrochemistry with carbon dioxide and hydrofluorocarbons (HFCs) being the most extensively studied. Recent advances have shown that it is possible to get well-resolved voltammetry in SCFs by suitable choice of the conditions and the electrolyte. In this review, we discuss the voltammetry obtained in these systems, studies of the double-layer capacitance, work on the electrodeposition of metals into high aspect ratio nanopores and the use of metallocenes as redox probes and standards in both supercritical carbon dioxide-acetonitrile and supercritical HFCs.

  4. Supercritical Airfoil Coordinates

    Data.gov (United States)

    National Aeronautics and Space Administration — Rectangular Supercritical Wing (Ricketts) - design and measured locations are provided in an Excel file RSW_airfoil_coordinates_ricketts.xls . One sheet is with Non...

  5. Supercritical fluid extraction of Beauvericin from maize.

    Science.gov (United States)

    Ambrosino, P; Galvano, F; Fogliano, V; Logrieco, A; Fresa, R; Ritieni, A

    2004-02-27

    Beauvericin (BEA), a supercritical fluid extraction with supercritical carbon dioxide from maize was investigated. Extraction efficiencies under several different extraction conditions were examined. Pressure, temperature, extraction time, organic modifier and water matrix content (10%) were investigated. The best extraction conditions were at a temperature of 60 degrees C, 3200psi, for 30min static extraction time and methanol as modifier solvent. Extraction recovery of 36% without modifier by adding water to the matrix in the extraction vessel (reproducibility relative standard deviations (R.S.D.)=3-5%) were recorded. Extraction recovery of 76.9% with methanol as co-solvent (reproducibility R.S.D.=3-5%) was obtained. Data shows that SFE gives a lower BEA recovery compared to conventional extraction protocol with organic solvents while SFE with modifier and conventional extraction yields are comparable. BEA extract contents were determined by high pressure liquid chromatography (HPLC) with a diode array detector (DAD) at 205nm and BEA peak confirmed by LC-MS. Acetonitrile-water as mobile phase and column C-18 were both tested. Instrumental and analytical parameters were optimized in the range linear interval from 1 to 500mgkg(-1) and reached a detection limit of 2ng.

  6. Preparing silica aerogel monoliths via a rapid supercritical extraction method.

    Science.gov (United States)

    Carroll, Mary K; Anderson, Ann M; Gorka, Caroline A

    2014-02-28

    A procedure for the fabrication of monolithic silica aerogels in eight hours or less via a rapid supercritical extraction process is described. The procedure requires 15-20 min of preparation time, during which a liquid precursor mixture is prepared and poured into wells of a metal mold that is placed between the platens of a hydraulic hot press, followed by several hours of processing within the hot press. The precursor solution consists of a 1.0:12.0:3.6:3.5 x 10(-3) molar ratio of tetramethylorthosilicate (TMOS):methanol:water:ammonia. In each well of the mold, a porous silica sol-gel matrix forms. As the temperature of the mold and its contents is increased, the pressure within the mold rises. After the temperature/pressure conditions surpass the supercritical point for the solvent within the pores of the matrix (in this case, a methanol/water mixture), the supercritical fluid is released, and monolithic aerogel remains within the wells of the mold. With the mold used in this procedure, cylindrical monoliths of 2.2 cm diameter and 1.9 cm height are produced. Aerogels formed by this rapid method have comparable properties (low bulk and skeletal density, high surface area, mesoporous morphology) to those prepared by other methods that involve either additional reaction steps or solvent extractions (lengthier processes that generate more chemical waste).The rapid supercritical extraction method can also be applied to the fabrication of aerogels based on other precursor recipes.

  7. Robust constraint on a drifting proton-to-electron mass ratio at z=0.89 from methanol observation at three radio telescopes.

    Science.gov (United States)

    Bagdonaite, J; Daprà, M; Jansen, P; Bethlem, H L; Ubachs, W; Muller, S; Henkel, C; Menten, K M

    2013-12-06

    A limit on a possible cosmological variation of the proton-to-electron mass ratio μ is derived from methanol (CH3OH) absorption lines in the benchmark PKS1830-211 lensing galaxy at redshift z=0.89 observed with the Effelsberg 100-m radio telescope, the Institute de Radio Astronomie Millimétrique 30-m telescope, and the Atacama Large Millimeter/submillimeter Array. Ten different absorption lines of CH3OH covering a wide range of sensitivity coefficients K(μ) are used to derive a purely statistical 1σ constraint of Δμ/μ=(1.5±1.5)×10(-7) for a lookback time of 7.5 billion years. Systematic effects of chemical segregation, excitation temperature, frequency dependence, and time variability of the background source are quantified. A multidimensional linear regression analysis leads to a robust constraint of Δμ/μ=(-1.0±0.8(stat)±1.0(sys))×10(-7).

  8. Robust Constraint on a Drifting Proton-to-Electron Mass Ratio at z=0.89 from Methanol Observation at Three Radio Telescopes

    CERN Document Server

    Bagdonaite, Julija; Jansen, Paul; Bethlem, Hendrick L; Ubachs, Wim; Muller, Sébastien; Henkel, Christian; Menten, Karl M

    2013-01-01

    A limit on a possible cosmological variation of the proton-to-electron mass ratio $\\mu$ is derived from methanol (CH$_3$OH) absorption lines in the benchmark PKS1830$-$211 lensing galaxy at redshift $z \\sim 0.89$ observed with the Effelsberg 100-m radio telescope, the IRAM 30-m telescope, and the ALMA telescope array. Ten different absorption lines of CH$_3$OH covering a wide range of sensitivity coefficients $K_{\\mu}$ are used to derive a purely statistical 1-$\\sigma$ constraint of $\\Delta\\mu/\\mu = (1.5 \\pm 1.5) \\times 10^{-7}$ for a lookback time of 7.5 billion years. Systematic effects of chemical segregation, excitation temperature, frequency dependence and time variability of the background source are quantified. A multi-dimensional linear regression analysis leads to a robust constraint of $\\Delta\\mu/\\mu = (-1.0 \\pm 0.8_{\\rm stat} \\pm 1.0_{\\rm sys}) \\times 10^{-7}$.

  9. Metal Nanoparticles Preparation In Supercritical Carbon Dioxide Solutions

    Energy Technology Data Exchange (ETDEWEB)

    Harry W. Rollins

    2004-04-01

    The novel optical, electronic, and/or magnetic properties of metal and semiconductor nanoparticles have resulted in extensive research on new methods for their preparation. An ideal preparation method would allow the particle size, size distribution, crystallinity, and particle shape to be easily controlled, and would be applicable to a wide variety of material systems. Numerous preparation methods have been reported, each with its inherent advantages and disadvantages; however, an ideal method has yet to emerge. The most widely applied methods for nanoparticle preparation include the sonochemical reduction of organometallic reagents,(1&2) the solvothermal method of Alivisatos,(3) reactions in microemulsions,(4-6) the polyol method (reduction by alcohols),(7-9) and the use of polymer and solgel materials as hosts.(10-13) In addition to these methods, there are a variety of methods that take advantage of the unique properties of a supercritical fluid.(14&15) Through simple variations of temperature and pressure, the properties of a supercritical fluid can be continuously tuned from gas-like to liquid-like without undergoing a phase change. Nanoparticle preparation methods that utilize supercritical fluids are briefly reviewed below using the following categories: Rapid Expansion of Supercritical Solutions (RESS), Reactive Supercritical Fluid Processing, and Supercritical Fluid Microemulsions. Because of its easily accessible critical temperature and pressure and environmentally benign nature, carbon dioxide is the most widely used supercritical solvent. Supercritical CO2 is unfortunately a poor solvent for many polar or ionic species, which has impeded its use in the preparation of metal and semiconductor nanoparticles. We have developed a reactive supercritical fluid processing method using supercritical carbon dioxide for the preparation of metal and metal sulfide particles and used it to prepare narrowly distributed nanoparticles of silver (Ag) and silver sulfide

  10. Characterization of cytochromes from Methanosarcina strain Göl and their involvement in electron transport during growth on methanol.

    Science.gov (United States)

    Kamlage, B; Blaut, M

    1992-01-01

    Methanosarcina strain Gö1 was tested for the presence of cytochromes. Low-temperature spectroscopy, hemochrome derivative spectroscopy, and redox titration revealed the presence of two b-type (b559 and b564) and two c-type (c547 and c552) cytochromes in membranes from Methanosarcina strain Gö1. The midpoint potentials determined were Em,7 = -135 +/- 5 and -240 +/- 11 mV (b-type cytochromes) and Em,7 = -140 +/- 10 and -230 +/- 10 mV (c-type cytochromes). The protoheme IX and the heme c contents were 0.21 to 0.24 and 0.09 to 0.28 mumol/g of membrane protein, respectively. No cytochromes were detectable in the cytoplasmic fraction. Of various electron donors and acceptors tested, only the reduced form of coenzyme F420 (coenzyme F420H2) and the heterodisulfide of coenzyme M and 7-mercaptoheptanoylthreonine phosphate (CoM-S-S-HTP) were capable of reducing and oxidizing the cytochromes at a high rate, respectively. Addition of CoM-S-S-HTP to reduced cytochromes and subsequent low-temperature spectroscopy revealed the oxidation of cytochrome b564. On the basis of these results, we suggest that one or several cytochromes participate in the coenzyme F420H2-dependent reduction of the heterodisulfide. PMID:1597414

  11. Drug delivery goes supercritical

    Directory of Open Access Journals (Sweden)

    Patrick J. Ginty

    2005-08-01

    Full Text Available In the field of drug delivery, the ability to control the size, morphology, and release of drug particles is fundamental to good targeting, but is often hampered by harsh processing conditions or inadequate methods; likewise for the processing of polymeric controlled-release systems. However, the use of supercritical fluids such as supercritical CO2 (scCO2 has provided a ‘clean’ and effective alternative to traditional methods of drug and polymer processing. In particular, scCO2 has a number of unique properties that make it possible to process both bioactive molecules and amorphous polymers without using toxic organic solvents or elevated temperatures. Here, we review the positive impact that supercritical fluids have had on the micronization, encapsulation, and impregnation of molecules of interest to both the pharmaceutical and biotechnology industries.

  12. Materials processing using supercritical fluids

    Directory of Open Access Journals (Sweden)

    Orlović Aleksandar M.

    2005-01-01

    Full Text Available One of the most interesting areas of supercritical fluids applications is the processing of novel materials. These new materials are designed to meet specific requirements and to make possible new applications in Pharmaceuticals design, heterogeneous catalysis, micro- and nano-particles with unique structures, special insulating materials, super capacitors and other special technical materials. Two distinct possibilities to apply supercritical fluids in processing of materials: synthesis of materials in supercritical fluid environment and/or further processing of already obtained materials with the help of supercritical fluids. By adjusting synthesis parameters the properties of supercritical fluids can be significantly altered which further results in the materials with different structures. Unique materials can be also obtained by conducting synthesis in quite specific environments like reversed micelles. This paper is mainly devoted to processing of previously synthesized materials which are further processed using supercritical fluids. Several new methods have been developed to produce micro- and nano-particles with the use of supercritical fluids. The following methods: rapid expansion of supercritical solutions (RESS supercritical anti-solvent (SAS, materials synthesis under supercritical conditions and encapsulation and coating using supercritical fluids were recently developed.

  13. Supercritical Synthesis of Biodiesel

    Directory of Open Access Journals (Sweden)

    Michel Vaultier

    2012-07-01

    Full Text Available The synthesis of biodiesel fuel from lipids (vegetable oils and animal fats has gained in importance as a possible source of renewable non-fossil energy in an attempt to reduce our dependence on petroleum-based fuels. The catalytic processes commonly used for the production of biodiesel fuel present a series of limitations and drawbacks, among them the high energy consumption required for complex purification operations and undesirable side reactions. Supercritical fluid (SCF technologies offer an interesting alternative to conventional processes for preparing biodiesel. This review highlights the advances, advantages, drawbacks and new tendencies involved in the use of supercritical fluids (SCFs for biodiesel synthesis.

  14. Capabilities and Limitations of an Association Theory for Chemicals in Liquid or Supercritical Solvents

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios

    2012-01-01

    . The capabilities of the model are illustrated in the first two case studies: the phase behavior of mixtures used in the oxidation of 2-octanol in supercritical CO2 and the investigation of systems containing acetone, methanol, water, chloroform, and methyl acetate. In each case, both correlations of vapor...

  15. 179 Extraction of Coal-tar Pitch by Supercritical Carbon Dioxide ...

    African Journals Online (AJOL)

    Meyer

    Extraction of Coal-tar Pitch by Supercritical Carbon Dioxide. .... methanol in vials that were cooled with a mixture of ice and sodium chloride to avoid the loss of .... The data produced by our experiments may be utilised in a kinetic study of the.

  16. Determination of the column hold-up volume in supercritical fluid chromatography using nitrous-oxide.

    Science.gov (United States)

    Vajda, Péter; Guiochon, Georges

    2013-09-27

    This study introduces a new tracer that is useful for the determination of the hold-up time or volume of packed columns, particularly of those used in supercritical fluid chromatography. The thermodynamic void volume of three columns packed with different adsorbents were determined using the weight difference method. These void volumes were used as the reference point in the further discussion. The hold-up volumes of these columns were determined under dynamic conditions, using nitrous oxide dissolved in methanol as the hold-up time marker. Changes in the hold-up volumes of these columns were monitored during changes of the volumetric flow rate of pure supercritical carbon dioxide and of dilute mixtures of organic modifier and supercritical carbon dioxide. The results suggest significant methanol enrichment on the adsorbent surface.

  17. [Optimization of supercritical fluid extraction of bioactive components in Ligusticum chuanxiong by orthogonal array design].

    Science.gov (United States)

    Hu, Li-Cui; Wu, Xun; Yang, Xue-Dong

    2013-10-01

    With the yields of ferulic acid, coniferylferulate, Z-ligustilide, senkyunolide A, butylidenephthalide, butylphthalide, senkyunolide I, senkyunolide H, riligustilide, levistolide A, and total pharmacologically active ingredient as evaluation indexes, the extraction of Ligusticum chuanxiong by supercritical fluid technology was investigated through an orthogonal experiment L9 (3(4)). Four factors, namely temperature, pressure, flow rate of carbon dioxide, co-solvent concentration of the supercritical fluid, were investigated and optimized. Under the optimized conditions, namely 65 degrees C of temperature, 35 MPa of pressure, 1 L x min(-1) of CO2 flow rate, 8% of co-solvent concetration, supercritical fluid extraction could achieve a better yield than the conventional reflux extraction using methanol. And the supercritical fluid extraction process was validated to be stable and reliable.

  18. Down-regulation of GST and CAT gene expression by methanolic ...

    African Journals Online (AJOL)

    DELL

    2013-07-03

    Jul 3, 2013 ... This in-vitro study reveals the effects of NS plant extract on GST and CAT gene ... with methanol using a Soxhlet apparatus as described previously. (Shafi et .... Extraction of Nigella sativa L. using Supercritical CO2: A Study of.

  19. Structural Transition in Supercritical Fluids

    Directory of Open Access Journals (Sweden)

    Boris I. Sedunov

    2011-01-01

    Full Text Available The extension of the saturation curve ( on the PT diagram in the supercritical region for a number of monocomponent supercritical fluids by peak values for different thermophysical properties, such as heat capacities and and compressibility has been studied. These peaks signal about some sort of fluid structural transition in the supercritical region. Different methods give similar but progressively diverging curves st( for this transition. The zone of temperatures and pressures near these curves can be named as the zone of the fluid structural transition. The outstanding properties of supercritical fluids in this zone help to understand the physical sense of the fluid structural transition.

  20. The Methanol Miracle

    Institute of Scientific and Technical Information of China (English)

    1995-01-01

    Methanol already makes a good fuel for camp stoves and even for a few cars. But in the future,say botanist Arthur Nonomura and biochemist Andrew Benson,methanol may fuel an agricultural revolution in hot and dry regions of the world. When the researchers recently sprayed diluted solutions of methanol on crops at Nonomura’s Arizona farm,they found they could double yields in some cases and halve water consumption in others.

  1. Critical temperatures and pressures of reacting mixture in synthesis of dimethyl carbonate with methanol and carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    Xing Cui Guo; Zhang Feng Qin; Guo Fu Wang; Jian Guo Wang

    2008-01-01

    Critical temperatures and pressures of nominal reacting mixture in synthesis of dimethyl carbonate (DMC)from methanol and carbon dioxide(quaternary mixture of carbon dioxide+methanol+water+DMC)were measured using a high-pressure view cell.The results suggested that the critical properties of the reacting mixture depended on the reaction extent as well as its initial composition(initial ratio of carbon dioxide to methanol).Such information is essential for determining the reaction conditions when one intends to carry out the synthesis of DMC with CO2 and methanol under supercritical conditions.

  2. Methanol Asinger's vision today

    CERN Document Server

    Bertau, Martin; Plass, Ludolf; Schmidt, Friedrich; Wernicke, Hans-Jürgen

    2014-01-01

    Methanol - The Chemical and Energy Feedstock of the Future offers a visionary yet unbiased view of methanol technology. Based on the groundbreaking 1986 publication ""Methanol"" by Friedrich Asinger, this book includes contributions by more than 40 experts from industry and academia. The authors and editors provide a comprehensive exposition of methanol chemistry and technology which is useful for a wide variety of scientists working in chemistry and energy related industries as well as academic researchers and even decision-makers and organisations concerned with the future of chemical and e

  3. The Methanol Economy Project

    Energy Technology Data Exchange (ETDEWEB)

    Olah, George [Univ. of Southern California, Los Angeles, CA (United States); Prakash, G. K. [Univ. of Southern California, Los Angeles, CA (United States)

    2014-02-01

    The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO2 capture using supported amines, co-electrolysis of CO2 and water to formate and syngas, decomposition of formate to CO2 and H2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

  4. Extraction of tannin by Acacia mearnsii with supercritical fluids

    Directory of Open Access Journals (Sweden)

    Marcia Regina Pansera

    2004-11-01

    Full Text Available Studies were carried out on solvent and supercritical extraction to obtain natural tannins. The results showed that the best co-solvent to extract tannin with CO2 supercritical was water with a concentration of 5.0% and the best trap rinse solvent was methanol.Neste trabalho foram utilizados dois processos de extração de tanino vegetal: extração a quente em aparelho Soxhlet e extração com CO2 supercítico. Os resultados mostraram que o melhor co-solvente para extração de taninos com CO2 supercrítico foi a água na concentração de 5% e o melhor solvente para lavagem do trap foi o metanol.

  5. Extraction of copper ions by supercritical carbon dioxide

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Complexation combined with supercritical fluid extraction was used to extract Cu2+ in this study. The effects of pressure, temperature, volume of CO2 on the efficiency of extraction were systematically investigated. At the optimum condition a 57.32% recovery was achieved. Addition of suitable amount of methanol(v/v = 5 % ) to the supercritical CO2 can increase in the extraction of Cu2+ (72.69 %, RSD = 2.12 %, n = 3). And the recovery can further increase in the presence of non-ionic surfactant Triton X-100 because of its function of solubilization. Surfactant was first used in the extraction of metal ions in the present study, and the results are satisfied (90.52%, RSD=2.20%, n =3).

  6. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  7. Supercritical solvent coal extraction

    Science.gov (United States)

    Compton, L. E. (Inventor)

    1984-01-01

    Yields of soluble organic extract are increased up to about 50% by the supercritical extraction of particulate coal at a temperature below the polymerization temperature for coal extract fragments (450 C.) and a pressure from 500 psig to 5,000 psig by the conjoint use of a solvent mixture containing a low volatility, high critical temperature coal dissolution catalyst such as phenanthrene and a high volatility, low critical temperature solvent such as toluene.

  8. Industrial applications and current trends in supercritical fluid technologies

    Directory of Open Access Journals (Sweden)

    Gamse Thomas

    2005-01-01

    Full Text Available Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop extraction or removal of pesticides from rice, activity in supercritical extraction producing total extract from the raw material or different fractions by using the fractionated separation of beverages (rum, cognac, whisky, wine, beer cider, of citrus oils and of lipids (fish oils, tall oil were also discussed. The main interest is still for the extraction of natural raw materials producing food ingredients, nutraceuticals and phytopharmaceuticals but also cleaning purposes were tested such as the decontamination of soils the removal of residual solvents from pharmaceutical products, the extraction of flame retardants from electronic waste or precision degreasing and cleaning of mechanical and electronic parts. An increasing interest obviously exists for impregnation purposes based on supercritical fluids behaviour, as well as for the dying of fibres and textiles. The production of fine particles in the micron and submicron range, mainly for pharmaceutical products is another important application of supercritical fluids. Completely new products can be produced which is not possible under normal conditions. Supercritical fluid technology has always had to compete with the widespread opinion that these processes are very expensive due to very high investment costs in comparison with classical low-pressure equipment. Thus the opinion is that these processes should be restricted to high-added value products. A cost estimation for different plant sizes and

  9. Effect of Co-solvent and Pressure on the Thermal Decomposition of 2, 2' Azobis - (isobutyronitrile) in Supercritical CO2

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The thermal decomposition of 2, 2'-azobis (isobutyronitrile) (AIBN) in supercritical CO2 with cosolvent methanol or cyclohexane has been studied by using UV/Vis spectroscopic method at 335.15 K and at 12.0 MPa and 14.0 MPa. Both of the cosolvents can accelerate the decomposition rate, and the effect of methanol is more significant than that of the cyclohexane.

  10. Effect of supercritical carbon dioxide on the enzymatic production of biodiesel from waste animal fat using immobilized Candida antarctica lipase B variant.

    Science.gov (United States)

    Pollardo, Aldricho Alpha; Lee, Hong-Shik; Lee, Dohoon; Kim, Sangyong; Kim, Jaehoon

    2017-09-09

    Waste animal fat is a promising feedstock to replace vegetable oil that widely used in commercial biodiesel process, however the high content of free fatty acid in waste fat makes it unfeasible to be processed with commercial base-catalytic process. Enzymatic process is preferable to convert waste fat into biodiesel since enzyme can catalyze both esterification of free fatty acid and transesterification of triglyceride. However, enzymatic reaction still has some drawbacks such as lower reaction rates than base-catalyzed transesterification and the limitation of reactant concentration due to the enzyme inhibition of methanol. Supercritical CO2 is a promising reaction media for enzyme-catalyzed transesterification to overcome those drawbacks. The transesterification of waste animal fat was carried out in supercritical CO2 with varied concentration of feedstock and methanol in CO2. The CO2 to feedstock mass ratio of 10:1 showed the highest yield compared to other ratios, and the highest FAME yield obtained from waste animal fat was 78%. The methanol concentration effect was also observed with variation 12%, 14%, and 16% of methanol to feedstock ratio. The best yield was 87% obtained at the CO2 to feedstock ratio of 10: 1 and at the methanol to feedstock ratio of 14% after 6 h of reaction. Enzymatic transesterification to produce biodiesel from waste animal fat in supercritical fluid media is a potential method for commercialization since it could enhance enzyme activity due to supercritical fluid properties to remove mass transfer limitation. The high yield of FAME when using high mass ratio of CO2 to oil showed that supercritical CO2 could increase the reaction and mass transfer rate while reducing methanol toxicity to enzyme activity. The increase of methanol concentration also increased the FAME yield because it might shift the reaction equilibrium to FAME production. This finding describes that the application of supercritical CO2 in the enzymatic reaction

  11. Reactions of inorganic nitrogen species in supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Dell`Orco, P.C. [Texas Univ., Austin, TX (United States)

    1994-12-31

    Redox reactions of nitrate salts with NH3 and methanol were studied in near-critical and supercritical water at 350 to 530 C and constant pressure of 302 bar. Sodium nitrate decomposition reactions were investigated at similar conditions. Reactions were conducted in isothermal tubular reactor under plug flow. For kinetic modeling, nitrate and nitrite reactants were lumped into an NO{sub x}{sup -} reactant; kinetic expressions were developed for MNO{sub 3}/NH{sub 4}X and sodium nitrate decomposition reactions. The proposed elementary reaction mechanism for MNO{sub 3}/NH{sub 4}X reaction indicated that NO{sub 2} was the primary oxidizing species and that N{sub 2}/N{sub 2}O selectivities could be determined by the form of MNO{sub 3} used. This suggest a nitrogen control strategy for use in SCWO (supercritical water oxidation) processes; nitrate or NH3 could be used to remove the other, at reaction conditions far less severe than required by other methods. Reactions of nitrate with methanol indicated that nitrate was a better oxidant than oxygen in supercritical water. Nitrogen reaction products included NH3 and nitrite, while inorganic carbon was the major carbon reaction product. Analysis of excess experiments indicated that the reaction at 475 C was first order in methanol concentration and second order in NO{sub x}{sup -} concentration. In order to determine phase regimes for these reactions, solubility of sodium nitrate was determined for some 1:1 nitrate electrolytes. Solubilities were measured at 450 to 525 C, from 248 to 302 bar. A semi-empirical solvation model was shown to adequately describe the experimental sodium nitrate solubilities. Solubilities of Li, Na, and K nitrates revealed with cations with smaller ionic radii had greater solubilities with nitrate.

  12. Methanol partial oxidation reformer

    Science.gov (United States)

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  13. Thermodynamic behaviour of supercritical matter.

    Science.gov (United States)

    Bolmatov, Dima; Brazhkin, V V; Trachenko, K

    2013-01-01

    Since their discovery in 1822, supercritical fluids have been of enduring interest and have started to be deployed in many important applications. Theoretical understanding of the supercritical state is lacking and is seen to limit further industrial deployment. Here we study thermodynamic properties of the supercritical state and discover that specific heat shows a crossover between two different regimes, an unexpected result in view of currently perceived homogeneity of supercritical state in terms of physical properties. We subsequently formulate a theory of system thermodynamics above the crossover, and find good agreement between calculated and experimental specific heat with no free-fitting parameters. In this theory, energy and heat capacity are governed by the minimal length of the longitudinal mode in the system only, and do not explicitly depend on system-specific structure and interactions. We derive a power law and analyse supercritical scaling exponents in the system above the Frenkel line.

  14. Qualitative Analysis of Transesterification of Waste Pig Fat in Supercritical Alcohols

    Directory of Open Access Journals (Sweden)

    Jeeban Poudel

    2017-02-01

    Full Text Available In this work, the characteristics of waste pig fat degradation using supercritical alcohols have been studied. Comparative analysis of the influence of supercritical methanol and supercritical ethanol as solvents on the transesterification was the primary focus of this research. The experiments were carried out with waste pig fat to alcohol weight ratios of 1:1.5 (molar ratio: 1:40.5 for methanol and 1:28 for ethanol, 1:2.0 (molar ratio: 1:54 for methanol and 1:37.5 for ethanol and 1:2.5 (molar ratio: 1:67.5 for methanol and 1:47 for ethanol at transesterification temperatures 250, 270 and 290 °C for holding time 0, 15, 30, 45 and 60 min. Increase in the transesterification and holding time increased the conversion while increase in alcohol amount from 1:1.5 to 1:2.0 and 1:2.5 had minimal effect on the conversion. Further, majority of the ester composition in using SCM as solvent falls in the carbon range of C17:0, C19:1 and C19:2 while that for SCE falls in the carbon range of C18:0, C20:1 and C20:2. Glycerol was only present while using SCM as solvent.

  15. Dietary methanol and autism.

    Science.gov (United States)

    Walton, Ralph G; Monte, Woodrow C

    2015-10-01

    The authors sought to establish whether maternal dietary methanol during pregnancy was a factor in the etiology of autism spectrum disorders. A seven item questionnaire was given to women who had given birth to at least one child after 1984. The subjects were solicited from a large primary care practice and several internet sites and separated into two groups - mothers who had given birth to a child with autism and those who had not. Average weekly methanol consumption was calculated based on questionnaire responses. 550 questionnaires were completed by women who gave birth to a non-autistic child. On average these women consumed 66.71mg. of methanol weekly. 161 questionnaires were completed by women who had given birth to an autistic child. The average estimated weekly methanol consumption for this group was 142.31mg. Based on the results of the Wilcoxon rank sum-test, we see a significant difference between the reported methanol consumption rates of the two groups. This study suggests that women who have given birth to an autistic child are likely to have had higher intake of dietary sources of methanol than women who have not. Further investigation of a possible link of dietary methanol to autism is clearly warranted.

  16. Catalytic upgrading of sugar fractions from pyrolysis oils in supercritical mono-alcohols over Cu doped porous metal oxide

    NARCIS (Netherlands)

    Yin, Wang; Venderbosch, Hendrikus; Bottari, Giovanni; Krawzcyk, Krzysztof K.; Barta, Katalin; Heeres, Hero Jan

    In this work, we report on the catalytic valorization of sugar fractions, obtained by aqueous phase extraction of fast pyrolysis oils, in supercritical methanol (scMeOH) and ethanol (scEtOH) over a copper doped porous metal oxide (Cu-PMO). The product mixtures obtained are, in principle, suitable

  17. Catalytic upgrading of sugar fractions from pyrolysis oils in supercritical mono-alcohols over Cu doped porous metal oxide

    NARCIS (Netherlands)

    Yin, Wang; Venderbosch, Hendrikus; Bottari, Giovanni; Krawzcyk, Krzysztof K.; Barta, Katalin; Heeres, Hero Jan

    2015-01-01

    In this work, we report on the catalytic valorization of sugar fractions, obtained by aqueous phase extraction of fast pyrolysis oils, in supercritical methanol (scMeOH) and ethanol (scEtOH) over a copper doped porous metal oxide (Cu-PMO). The product mixtures obtained are, in principle, suitable fo

  18. Preparation of PMMA Foam by Supercritical CO2 with Ethanol

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Supercritical CO2 with ethanol as blowing agent foamed poly(methylmethacrylate) (PMMA) fiber at 308.15K and in the pressure range from 12-15MPa. The foam structure was detected using scanning electron microscope. It was found that the concentration of ethanol in the fluid is a major parameter to affect the foam structure.

  19. Liquefaction of Typha latifolia by supercritical fluid extraction.

    Science.gov (United States)

    Aysu, Tevfik; Turhan, Mehmet; Küçük, Mehmet Maşuk

    2012-03-01

    Milled Typha latifolia stalk mill was converted to liquid products by using organic solvents (methanol, ethanol, acetone and 2-butanol) with catalysts (10% NaOH or Na(2)CO(3)) and without catalyst in an autoclave at temperatures of 518, 538 and 558 K. The products were extracted by liquid-liquid extraction (benzene and diethyl ether). The percentage yields from supercritical methanol, ethanol, 2-butanol and acetone conversions were 55.0, 58.5, 62.7 and 70.5 at 538 K, respectively. In the catalytic run with NaOH, the highest conversion was obtained by using ethanol as a solvent at the same temperature. Conversion yields were analyzed by GC-MS. The aim of the present study was to obtain an alternative for petroleum derived fuels or chemical raw materials. Copyright © 2011 Elsevier Ltd. All rights reserved.

  20. Extraction of Genistein from Sophora flavescens with Supercritical Carbon Dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Han, Chang-Nam; Kang, Choon-Hyoung [Chonnam National University, Gwangju (Korea, Republic of)

    2015-08-15

    This study was directed to finding an optimum extraction condition of genistein from the S. flavescens with supercritical carbon dioxide as a solvent. In this effort, effects of the extraction conditions including pressure, temperature and a co-solvent on the extraction efficiency were investigated. The aqueous ethanol and methanol solutions were used as co-solvents while the tested operating pressure and temperature ranges were from 200 bar to 300 bar and from 308.15 K to 323.15 K, respectively. The concentration of genistein was determined by means of HPLC equipped with a UV detector. From the results, it was observed that an increase in pressure led to the higher extraction efficiency. Further, methanol showed better performance as a co-solvent than ethanol. The DPPH radical scavenging activities were measured to compare antioxidant activities of S. flavescens extracts.

  1. Oxidation behavior of Incoloy 800 under simulated supercritical water conditions

    Energy Technology Data Exchange (ETDEWEB)

    Fulger, M. [Institute for Nuclear Research Pitesti, POB 78, Campului Street, No. 1, 115400 Mioveni (Romania)], E-mail: manuela.fulger@nuclear.ro; Ohai, D.; Mihalache, M.; Pantiru, M. [Institute for Nuclear Research Pitesti, POB 78, Campului Street, No. 1, 115400 Mioveni (Romania); Malinovschi, V. [University of Pitesti, Research Center for Advanced Materials, Targul din Vale Street, No. 1, 110040 Pitesti (Romania)

    2009-03-31

    For a correct design of supercritical water-cooled reactor (SCWR) components, data regarding the behavior of candidate materials in supercritical water are necessary. Corrosion has been identified as a critical problem because the high temperature and the oxidative nature of supercritical water may accelerate the corrosion kinetics. The goal of this paper is to investigate the oxidation behavior of Incoloy 800 exposed in autoclaves under supercritical water conditions for up to 1440 h. The exposure conditions (thermal deaerated water, temperatures of 723, 773, 823 and 873 K and a pressure of 25 MPa) have been selected as relevant for a supercritical power plant concept. To investigate the structural changes of the oxide films, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and electrochemical impedance spectroscopy (EIS) analyses were used. Results show changes in the oxides chemical composition, microstructure and thickness versus testing conditions (pressure, temperature and time). The oxide films are composed of two layers: an outer layer enriched in Fe oxide and an inner layer enriched in Cr and Ni oxides corresponding to small cavities supposedly due to internal oxidation.

  2. Methanol Cannon Demonstrations Revisited.

    Science.gov (United States)

    Dolson, David A.; And Others

    1995-01-01

    Describes two variations on the traditional methanol cannon demonstration. The first variation is a chain reaction using real metal chains. The second example involves using easily available components to produce sequential explosions that can be musical in nature. (AIM)

  3. Bifunctional activation of a direct methanol fuel cell

    Science.gov (United States)

    Kulikovsky, A. A.; Schmitz, H.; Wippermann, K.; Mergel, J.; Fricke, B.; Sanders, T.; Sauer, D. U.

    We report a novel method for performance recovery of direct methanol fuel cells. Lowering of air flow rate below a critical value turns the cell into bifunctional regime, when the oxygen-rich part of the cell generates current while the rest part works in electrolysis mode (electrolytic domain). Upon restoring the normal (super-critical) air flow rate, the galvanic performance of the electrolytic domain increases. This recovery effect is presumably attributed to Pt surface cleaning on the cathode with the simultaneous increase in catalyst utilization on the anode.

  4. Supercritical fluid extraction of vapor-deposited pyrene from carbonaceous coal stack ash.

    Science.gov (United States)

    Mauldin, R F; Vienneau, J M; Wehry, E L; Mamantov, G

    1990-11-01

    The efficiencies of extraction of vapor-deposited pyrene from a high-carbon coal stack ash by Soxhlet extraction with methanol, ultrasonic extraction with toluene, acid pretreatment and subsequent ultrasonic extraction with toluene, batch extraction with toluene, and supercritical fluid extraction (SFE) are compared. SFE using CO(2) or isobutane yielded extraction recoveries virtually identical with those obtained using ultrasonic or Soxhlet extraction processes. Collection of the SFE extract was performed by expansion into a solvent or onto the head of a gas chromatography (GC) column. No loss of extracted pyrene was observed upon collection of methanol-modified CO(2) SFE by expansion into methanol. Also, no loss of pure CO(2) SFE extract was observed upon collection on the head of a GC column. However, use of a methanol or toluene modifier for CO(2) SFE directly coupled to GC effected complete loss of extracted pyrene.

  5. ENGINEERING BULLETIN: SUPERCRITICAL WATER OXIDATION

    Science.gov (United States)

    This engineering bulletin presents a description and status of supercritical water oxidation technology, a summary of recent performance tests, and the current applicability of this emerging technology. This information is provided to assist remedial project managers, contractors...

  6. Development of new membrane materials for direct methanol fuel cells

    NARCIS (Netherlands)

    Yildirim, Mustafa Hakan

    2009-01-01

    Development of new membrane materials for direct methanol fuel cells Direct methanol fuel cells (DMFCs) can convert the chemical energy of a fuel directly into electrical energy with high efficiency and low emission of pollutants. DMFCs can be used as the power sources to portable electronic devices

  7. Development of new membrane materials for direct methanol fuel cells

    NARCIS (Netherlands)

    Yildirim, M.H.

    2009-01-01

    Development of new membrane materials for direct methanol fuel cells Direct methanol fuel cells (DMFCs) can convert the chemical energy of a fuel directly into electrical energy with high efficiency and low emission of pollutants. DMFCs can be used as the power sources to portable electronic devices

  8. Extending the range of supercritical fluid chromatography by use of water-rich modifiers.

    Science.gov (United States)

    Liu, Jinchu; Regalado, Erik L; Mergelsberg, Ingrid; Welch, Christopher J

    2013-08-14

    In this study we investigate the recently reported use of water-containing modifiers for separation and purification of hydrophilic compounds by supercritical fluid chromatography. Improved peak shape is obtained for a variety of glycosides and otherwise hydrophilic compounds when 5% water is added to the methanol co-solvent used in SFC separations, and examples of the use of this approach in preparative SFC purifications are presented.

  9. Supercritical fluid technology

    Energy Technology Data Exchange (ETDEWEB)

    Penninger, J.M.L.; McHugh, M.A.; Radosz, M.; Krukonis, V.J.

    1985-01-01

    This book presents the state-of-the-art in the science and technology of supercritical fluid (scf) processing. Current research as described in the book, focuses on developments in equations of state for binary and multicomponent mixtures (including polymer solutions), solubility measurements at near-critical conditions, measurements of critical properties of binary mixtures and their correlation with equations of state. Progress in thermodynamics, coupled with advances in the design and construction of high pressure equipment, has opened up a wide avenue of commercial application (e.g. decaffeination of coffee beans, extractions of flavours and spices, purification of pharmaceutical products, separations of polymeric materials, deodorization and deacidification of vegetable oils, fractionation of fatty acids, coal liquefaction, wood delignitication, etc.)

  10. Hollow nano-particles formation for CuO-CeO2-ZrO2 via a supercritical anti-solvent process

    Institute of Scientific and Technical Information of China (English)

    姜浩锡; 周佳丽; 孙焕花; 李永辉; 张敏华

    2016-01-01

    Hollow CuO-CeO2-ZrO2nano-particles were prepared with supercritical anti-solvent apparatus by using methanol as sol-vent and supercritical carbon dioxide as anti-solvent. Two key factors (i.e., pressure and temperature) were investigated to explore the effects of catalyst structure and physic-chemical properties (i.e., morphology, reducing property, oxygen storage capacity and specific surface area). The resulting materials were characterized with X-ray diffraction (XRD), high resolution transmission electron micros-copy (HRTEM), Brunauer-Emmett-Teller (BET),hydrogen temperature programmed reduction (H2-TPR) and oxygen storage capac-ity (OSC) measurement, respectively. The experimental results showed that lower temperatures promoted production of hollow struc-ture nano-particulates. The particle morphology also changed significantly, i.e. the solid construction was first transferred to hollow structure then back to solid construction. The optimal conditions for obtaining hollow nano-particles were determined at 45 °C, 18.0–24.0 MPa.

  11. Supercritical carbon dioxide-based sterilization of decellularized heart valves.

    Science.gov (United States)

    Hennessy, Ryan S; Jana, Soumen; Tefft, Brandon J; Helder, Meghana R; Young, Melissa D; Hennessy, Rebecca R; Stoyles, Nicholas J; Lerman, Amir

    2017-02-01

    The goal of this research project encompasses finding the most efficient and effective method of decellularized tissue sterilization. Aortic tissue grafts have been utilized to repair damaged or diseased valves. Although, the tissues for grafting are collected aseptically, it does not eradicate the risk of contamination nor disease transfer. Thus, sterilization of grafts is mandatory. Several techniques have been applied to sterilize grafts; however, each technique shows drawbacks. In this study, we compared several sterilization techniques: supercritical carbon dioxide, electrolyzed water, gamma radiation, ethanol-peracetic acid, and hydrogen peroxide for impact on the sterility and mechanical integrity of porcine decellularized aortic valves. Valve sterility was characterized by histology, microbe culture, and electron microscopy. Uniaxial tensile testing was conducted on the valve cusps along their circumferential orientation to study these sterilization techniques on their integrity. Ethanol-peracetic acid and supercritical carbon dioxide treated valves were found to be sterile. The tensile strength of supercritical carbon dioxide treated valves (4.28 ± 0.22 MPa) was higher to those valves treated with electrolyzed water, gamma radiation, ethanol-peracetic acid and hydrogen peroxide (1.02 ± 0.15, 1.25 ± 0.25, 3.53 ± 0.41 and 0.37 ± 0.04 MPa, respectively). Superior sterility and integrity were found in the decellularized porcine aortic valves with supercritical carbon dioxide sterilization. This sterilization technique may hold promise for other decellularized soft tissues. Sterilization of grafts is essential. Supercritical carbon dioxide, electrolyzed water, gamma radiation, ethanol-peracetic acid, and hydrogen peroxide techniques were compared for impact on sterility and mechanical integrity of porcine decellularized aortic valves. Ethanol-peracetic acid and supercritical carbon dioxide treated valves were found to be sterile using histology, microbe

  12. Nanotechnology and supercritical fluids | Hamidreza | Journal of ...

    African Journals Online (AJOL)

    Several techniques have been proposed to produce nanomaterials using ... of the supercritical based techniques applied to the production of nanoparticles materials. Keywords: Supercritical fluids; Nanoparticles; SCF technology; RESS; SAS.

  13. Efficient separation of curcumin, demethoxycurcumin, and bisdemethoxycurcumin from turmeric using supercritical fluid chromatography: From analytical to preparative scale.

    Science.gov (United States)

    Song, Wei; Qiao, Xue; Liang, Wen-fei; Ji, Shuai; Yang, Lu; Wang, Yuan; Xu, Yong-wei; Yang, Ying; Guo, De-an; Ye, Min

    2015-10-01

    Curcumin is the major constituent of turmeric (Curcuma longa L.). It has attracted widespread attention for its anticancer and anti-inflammatory activities. The separation of curcumin and its two close analogs, demethoxycurcumin and bisdemethoxycurcumin, has been challenging by conventional techniques. In this study, an environmentally friendly method based on supercritical fluid chromatography was established for the rapid and facile separation of the three curcuminoids directly from the methanol extract of turmeric. The method was first developed and optimized by ultra performance convergence chromatography, and was then scaled up to preparative supercritical fluid chromatography. Eluted with supercritical fluid CO2 containing 8-15% methanol (containing 10 mM oxalic acid) at a flow rate of 80 mL/min, curcumin, demethoxycurcumin and bisdemethoxycurcumin could be well separated on a Viridis BEH OBD column (Waters, 250 mm × 19 mm, 5 μm) within 6.5 min. As a result, 20.8 mg of curcumin (97.9% purity), 7.0 mg of demethoxycurcumin (91.1%), and 4.6 mg of bisdemethoxycurcumin (94.8%) were obtained after a single step of supercritical fluid chromatography separation with a mean recovery of 76.6%. Showing obvious advantages in low solvent consumption, large sample loading, and easy solvent removal, supercritical fluid chromatography was proved to be a superior technique for the efficient separation of natural products.

  14. Biodiesel production with continuous supercritical process: non-catalytic transesterification and esterification with or without carbon dioxide.

    Science.gov (United States)

    Tsai, Yu-Ting; Lin, Ho-mu; Lee, Ming-Jer

    2013-10-01

    The non-catalytic transesterification of refined sunflower oil with supercritical methanol, in the presence of carbon dioxide, was conducted in a tubular reactor at temperatures from 553.2 to 593.2K and pressures up to 25.0 MPa. The FAME yield can be achieved up to about 0.70 at 593.2 K and 10.0 MPa in 23 min with methanol:oil of 25:1 in molar ratio. The effect of adding CO2 on the FAME yield is insignificant. The kinetic behavior of the non-catalytic esterification and transesterification of oleic acid or waste cooking oil (WCO) with supercritical methanol was also investigated. By using the supercritical process, the presence of free fatty acid (FFA) in WCO gives positive contribution to FAME production. The FAME yield of 0.90 from WCO can be achieved in 13 min at 573.2K. The kinetic data of supercritical transesterification and esterifaication were correlated well with a power-law model. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Electronic structures of active sites on metal oxide surfaces: Definition of the Cu/ZnO methanol synthesis catalyst by photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Solomon, E.I.; Jones, P.M.; May, J.A. (Stanford Univ., CA (United States). Dept. of Chemistry)

    1993-12-01

    The focus of this review is on the use of photoelectron spectroscopy (PES) to study the interaction of small molecules (particularly carbon monoxide) with metal ion sites on metal oxide surfaces. There have been numerous photoemission studies of chemisorption on metal surfaces. However, it is important to note that while metal oxides are involved in many heterogeneous catalytic processes, only a limited number of electron spectroscopic studies of chemically relevant molecules on metal oxide surfaces have appeared. The paper contains the following sections: The electronic structure of clean ZnO surfaces -- variable-energy photoelectron spectroscopy; CO chemisorption on ZnO surfaces; geometric structures for CO binding to the four chemically different surfaces of ZnO; electronic structure of the CO/ZnO surface complex; nature of copper sites on ZnO surfaces; electronic structures of CO bonding to d[sup 10] metal ion sites; relevance to catalysis; and summary and future directions. 185 refs.

  16. Direct Methanol Fuel Cell, DMFC

    Directory of Open Access Journals (Sweden)

    Amornpitoksuk, P.

    2003-09-01

    Full Text Available Direct Methanol Fuel Cell, DMFC is a kind of fuel cell using methanol as a fuel for electric producing. Methanol is low cost chemical substance and it is less harmful than that of hydrogen fuel. From these reasons it can be commercial product. The electrocatalytic reaction of methanol fuel uses Pt-Ru metals as the most efficient catalyst. In addition, the property of membrane and system designation are also effect to the fuel cell efficient. Because of low power of methanol fuel cell therefore, direct methanol fuel cell is proper to use for the energy source of small electrical devices and vehicles etc.

  17. A simple analysis of the stable field profile in the supercritical TEA

    DEFF Research Database (Denmark)

    Jeppesen, Palle; Jeppsson, B.

    1973-01-01

    An analytical investigation supported by numerical calculations has been performed of the stable field profile in a supercritical diffusion-stabilized n-GaAs transferred electron amplifier (TEA) with ohmic contacts. In the numerical analysis, the field profile is determined by solving the steady......}{2}} (n_{0}L)^{frac{1}{2}}. Those results contribute to the understanding of the highn_{0}L-product switch and the stability of the supercritical TEA....

  18. Dynamic transition in supercritical iron.

    Science.gov (United States)

    Fomin, Yu D; Ryzhov, V N; Tsiok, E N; Brazhkin, V V; Trachenko, K

    2014-11-26

    Recent advance in understanding the supercritical state posits the existence of a new line above the critical point separating two physically distinct states of matter: rigid liquid and non-rigid gas-like fluid. The location of this line, the Frenkel line, remains unknown for important real systems. Here, we map the Frenkel line on the phase diagram of supercritical iron using molecular dynamics simulations. On the basis of our data, we propose a general recipe to locate the Frenkel line for any system, the recipe that importantly does not involve system-specific detailed calculations and relies on the knowledge of the melting line only. We further discuss the relationship between the Frenkel line and the metal-insulator transition in supercritical liquid metals. Our results enable predicting the state of supercritical iron in several conditions of interest. In particular, we predict that liquid iron in the Jupiter core is in the "rigid liquid" state and is highly conducting. We finally analyse the evolution of iron conductivity in the core of smaller planets such as Earth and Venus as well as exoplanets: as planets cool off, the supercritical core undergoes the transition to the rigid-liquid conducting state at the Frenkel line.

  19. Supercritical Fluid Reactions for Coal Processing

    Energy Technology Data Exchange (ETDEWEB)

    Charles A. Eckert

    1997-11-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we developed a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as one model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane. The Diels-Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) was selected as a second model system, and it was investigated in supercritical carbon dioxide.

  20. Preparation of Aromatic Polycarbonate Nanoparticles using Supercritical Carbon Dioxide

    Science.gov (United States)

    Lee, Jun-Young; Song, Cheong-Hun; Kim, Joong-In; Kim, Jung-Hyun

    2002-04-01

    A novel synthetic process for producing aromatic polycarbonate (PC) nanoparticles using supercritical CO2 was developed. The objective of the present research work was to synthesize high molecular weight PC nanoparticles using transesterification between bisphenol-A (BPA) and diphenyl carbonate (DPC) in supercritical CO2 which is an excellent plasticizing agent and a good solvent for phenol, a by-product of the reaction. Poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) tri-block copolymer with CO2-phobic anchor and CO2-philic tail group was used as a stabilizer for the preparation of stable dispersions of BPA-DPC mixture in a CO2 continuous phase. As the reaction was proceeding, phenol formed from the reaction was dissolved and diffused into supercritical CO2 phase. The PC nanoparticles were isolated by simple venting of the supercritical CO2 from the reactor. Spherical morphology of PC particles was confirmed by scanning electron microscopy. Particle size and morphology of PC particles were modified upon variation of the process conditions. The resulting PC particles with a nano-size of 30-140 nm have a high molecular weight ( M w) of 3.1×105 (g/mol).

  1. The toxicity of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Tephly, T.R. (Univ. of Iowa, Iowa City (USA))

    1991-01-01

    Methanol toxicity in humans and monkeys is characterized by a latent period of many hours followed by a metabolic acidosis and ocular toxicity. This is not observed in most lower animals. The metabolic acidosis and blindness is apparently due to formic acid accumulation in humans and monkeys, a feature not seen in lower animals. The accumulation of formate is due to a deficiency in formate metabolism which is, in turn, related, in part, to low hepatic tetrahydrofolate (H{sub 4}folate). An excellent correlation between hepatic H{sub 4} folate and formate oxidation rates has been shown within and across species. Thus, humans and monkeys possess low hepatic H{sub 4}folate levels, low rates of formate oxidation and accumulation of formate after methanol. Formate, itself, produces blindness in monkeys in the absence of metabolic acidosis. In addition to low hepatic H{sub 4}folate concentrations, monkeys and humans also have low hepatic 10-formyl H{sub 4}folate dehydrogenase levels, the enzyme which is the ultimate catalyst for conversion of formate to carbon dioxide. This review presents the basis for the role of folic acid-dependent reactions in the regulation of methanol toxicity.

  2. The Revised Version of Class I Methanol Maser Catalog

    CERN Document Server

    Val'tts, I E; Bayandina, O S

    2010-01-01

    The revised version of the class I methanol maser catalog is presented. It contains 182 sources - new class I methanol masers detected in the direction of EGOs were added to the previous number (~160 sources have been published in the first version of this catalog - see reference in the text). Electronic version has been generated in the form of html file - http://www.asc.rssi.ru/MMI. A statistical analysis was carried out within 2' around a maser position to find an identification of class I methanol masers with any objects typical for star-forming regions - UCHII regions, IRAS sources, bipolar outflows, CS lines as of dense gas tracer, masers (class II methanol masers, OH and H2O) and EGO. None of the bipolar outflow, already registered in the direction of class I methanol maser, did not coincide with EGO. The result is submitted in a form of a diagram.

  3. Removing Solids From Supercritical Water

    Science.gov (United States)

    Hong, Glenn T.

    1992-01-01

    Apparatus removes precipitated inorganic salts and other solids in water-recycling process. Designed for use with oxidation in supercritical water which treats wastes and yields nearly pure water. Heating coils and insulation around vessel keep it hot. Locking bracket seals vessel but allows it to be easily opened for replacement of filled canisters.

  4. Electromagnetic Whistler Precursors at Supercritical Interplanetary Shocks

    Science.gov (United States)

    Wilson, L. B., III

    2012-01-01

    We present observations of electromagnetic precursor waves, identified as whistler mode waves, at supercritical interplanetary shocks using the Wind search coil magnetometer. The precursors propagate obliquely with respect to the local magnetic field, shock normal vector, solar wind velocity, and they are not phase standing structures. All are right-hand polarized with respect to the magnetic field (spacecraft frame), and all but one are right-hand polarized with respect to the shock normal vector in the normal incidence frame. Particle distributions show signatures of specularly reflected gyrating ions, which may be a source of free energy for the observed modes. In one event, we simultaneously observe perpendicular ion heating and parallel electron acceleration, consistent with wave heating/acceleration due to these waves.

  5. Etching of glass microchips with supercritical water.

    Science.gov (United States)

    Karásek, Pavel; Grym, Jakub; Roth, Michal; Planeta, Josef; Foret, František

    2015-01-07

    A novel method of etching channels in glass microchips with the most tunable solvent, water, was tested as an alternative to common hydrogen fluoride-containing etchants. The etching properties of water strongly depend on temperature and pressure, especially in the vicinity of the water critical point. The chips were etched at the subcritical, supercritical and critical temperature of water, and the resulting channel shape, width, depth and surface morphology were studied by scanning electron microscopy and 3D laser profilometry. Channels etched with the hot water were compared with the chips etched with standard hydrogen fluoride-containing solution. Depending on the water pressure and temperature, the silicate dissolved from the glass could be re-deposited on the channel surface. This interesting phenomenon is described together with the conditions necessary for its utilization. The results illustrate the versatility of pure water as a glass etching and surface morphing agent.

  6. Water-methanol separation with carbon nanotubes and electric fields

    Science.gov (United States)

    Winarto, Affa; Takaiwa, Daisuke; Yamamoto, Eiji; Yasuoka, Kenji

    2015-07-01

    diameter. In contrast, under an electric field, water molecules strongly prefer to occupy the CNTs over methanol molecules, resulting in a separation effect for water. More interestingly, the separation effect for water does not decrease with increasing CNT diameter. Formation of water structures in CNTs induced by an electric field has an important role in the separation of water from methanol. Electronic supplementary information (ESI) available: Molecule structures in carbon nanotubes. Water molecules vs. methanol molecules in carbon nanotubes under electric field. See DOI: 10.1039/c5nr02182k

  7. Supercritical carbon dioxide extraction of Mentha pulegium L. essential oil.

    Science.gov (United States)

    Aghel, Nasrin; Yamini, Yadollah; Hadjiakhoondi, Abbas; Pourmortazavi, Seied Mahdi

    2004-02-06

    The dependence of Mentha pulegium L. (pennyroyal) essential oil composition, obtained by supercritical carbon dioxide (SC-CO(2)), with the following parameters: pressure, temperature, extraction time (dynamic), and modifier (methanol) was studied. The results were also compared with those obtained by conventional hydrodistillation method in laboratory conditions. Regarding the percentages of menthone (30.3%) and pulegone (52.0%), the optimum SFE results were obtained at the following experimental conditions: pressure=100atm, T=35 degrees C, dynamic time=10min, and V(modifier)=0mul. The results of hydrodistillation showed that the major components of M. pulegium L. were pulegone (37.8%), menthone (20.3%), and piperitenone (6.8%). The evaluation of the composition of each extract was performed by gas chromatography-mass spectrometry.

  8. Synthesis pf dimethyl carbonate in supercritical carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Ballivet-Tkatchenko, D.; Plasseraud, L. [Universite de Bourgogne-UFR Sciences et Techniques, Dijon (France). Lab. de Synthese et Electrosynthese Organometalliques]. E-mail: ballivet@u-bourgogne.fr; Ligabue, R.A. [Pontificia Univ. Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil). Dept. de Quimica Pura

    2006-01-15

    The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu{sub 3}SnOCH{sub 3}, n-Bu{sub 2}Sn(OCH{sub 3}){sub 2}, and [n-Bu{sub 2}(CH{sub 3}O)Sn]{sub 2}O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO{sub 2} pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO{sub 2} pressure higher than 16 MPa. Under these conditions, CO{sub 2} acted as a reactant and a solvent. (author)

  9. Diffusion Limited Supercritical Water Oxidation (SCWO) in Microgravity Environments

    Science.gov (United States)

    Hicks, M. C.; Lauver, R. W.; Hegde, U. G.; Sikora, T. J.

    2006-01-01

    Tests designed to quantify the gravitational effects on thermal mixing and reactant injection in a Supercritical Water Oxidation (SCWO) reactor have recently been performed in the Zero Gravity Facility (ZGF) at NASA s Glenn Research Center. An artificial waste stream, comprising aqueous mixtures of methanol, was pressurized to approximately 250 atm and then heated to 450 C. After uniform temperatures in the reactor were verified, a controlled injection of air was initiated through a specially designed injector to simulate diffusion limited reactions typical in most continuous flow reactors. Results from a thermal mapping of the reaction zone in both 1-g and 0-g environments are compared. Additionally, results of a numerical model of the test configuration are presented to illustrate first order effects on reactant mixing and thermal transport in the absence of gravity.

  10. Supercritical CO2 extraction of essential oils from Chamaecyparis obtusa.

    Science.gov (United States)

    Jin, Yinzhe; Han, Dandan; Tian, Minglei; Row, Kyung-Ho

    2010-03-01

    Supercritical carbon dioxide (SC-CO2) extraction and hydrodistillation (HD) were used to determine the essential oil composition of the trunks and leaves of Chamaecyparis obtusa. The optimal extraction conditions for the oil yield within the experimental range of variables examined were temperature 50 degrees C, pressure 12 MPa, carbon dioxide flow rate 40 mL/min and extraction time 90 min. The maximum measured extraction yield was 2.9%. Entrainer solvents, such as methanol in water, had no additional effect on the extraction of essential oils. The chemical composition of the essential oils was analyzed by GC-MS. The major components were alpha-terpinyl acetate (>10.9%), 1-muurolol (>13.2%) and elemol (>8.1%). Sesquiterpenoids formed the major class of compounds present.

  11. Synthesis of dimethyl carbonate in supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    D. Ballivet-Tkatchenko

    2006-03-01

    Full Text Available The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu3SnOCH3, n-Bu2Sn(OCH32 , and [n-Bu2(CH3OSn]2 O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO2 pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO2 pressure higher than 16 MPa. Under these conditions, CO2 acted as a reactant and a solvent.

  12. Biological conversion of biogas to methanol using methanotrophs isolated from solid-state anaerobic digestate.

    Science.gov (United States)

    Sheets, Johnathon P; Ge, Xumeng; Li, Yueh-Fen; Yu, Zhongtang; Li, Yebo

    2016-02-01

    The aim of this work was to isolate methanotrophs (methane oxidizing bacteria) that can directly convert biogas produced at a commercial anaerobic digestion (AD) facility to methanol. A methanotrophic bacterium was isolated from solid-state anaerobic digestate. The isolate had characteristics comparable to obligate methanotrophs from the genus Methylocaldum. This newly isolated methanotroph grew on biogas or purified CH4 and successfully converted biogas from AD to methanol. Methanol production was achieved using several methanol dehydrogenase (MDH) inhibitors and formate as an electron donor. The isolate also produced methanol using phosphate with no electron donor or using formate with no MDH inhibitor. The maximum methanol concentration (0.43±0.00gL(-1)) and 48-h CH4 to methanol conversion (25.5±1.1%) were achieved using biogas as substrate and a growth medium containing 50mM phosphate and 80mM formate.

  13. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-01-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 seconds. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  14. Atmospheric methanol measurement using selective catalytic methanol to formaldehyde conversion

    Directory of Open Access Journals (Sweden)

    S. J. Solomon

    2005-05-01

    Full Text Available A novel atmospheric methanol measurement technique, employing selective gas-phase catalytic conversion of methanol to formaldehyde followed by detection of the formaldehyde product, has been developed and tested. The effects of temperature, gas flow rate, gas composition, reactor-bed length, and reactor-bed composition on the methanol conversion efficiency of a molybdenum-rich, iron-molybdate catalyst [Mo-Fe-O] were studied. Best results were achieved using a 1:4 mixture (w/w of the catalyst in quartz sand. Optimal methanol to formaldehyde conversion (>95% efficiency occurred at a catalyst housing temperature of 345°C and an estimated sample-air/catalyst contact time of <0.2 s. Potential interferences arising from conversion of methane and a number of common volatile organic compounds (VOC to formaldehyde were found to be negligible under most atmospheric conditions and catalyst housing temperatures. Using the new technique, atmospheric measurements of methanol were made at the University of Bremen campus from 1 to 15 July 2004. Methanol mixing ratios ranged from 1 to 5 ppb with distinct maxima at night. Formaldehyde mixing ratios, obtained in conjunction with methanol by periodically bypassing the catalytic converter, ranged from 0.2 to 1.6 ppb with maxima during midday. These results suggest that selective, catalytic methanol to formaldehyde conversion, coupled with existing formaldehyde measurement instrumentation, is an inexpensive and effective means for monitoring atmospheric methanol.

  15. Supercritical fluid chromatography for the separation of isoflavones.

    Science.gov (United States)

    Ganzera, Markus

    2015-03-25

    The first protocol for the analysis of isoflavones by supercritical fluid chromatography is reported. Optimum results were obtained on an Acquity UPC(2) BEH 1.7 μm column, using a solvent gradient of supercritical carbon dioxide and methanol (with phosphoric acid as additive) for elution. The method enables the baseline separation of nine isoflavones (aglyca and glycosides) in 8 min, and is suitable for their quantitative determination in dietary supplements containing soy (Glycine max), red glover (Trifolium pratense) and kudzu (Pueraria lobata). Method validation confirmed that the assay is selective, linear (R(2)≥0.9994), accurate (recovery rates from 97.6 to 102.4%), as well as precise on the short- and long-term level (intra-day precision ≤2.1%), and shows an on-column detection limit of 0.2 ng and below. This, together with an excellent performance shown in the analysis of real samples, indicates that SFC is well suited for the fast and accurate determination of isoflavones in complex matrices. Disadvantages compared to the established approaches were not observed, so that SFC has to be considered in this case as an (at least) equivalent analytical alternative.

  16. Supercritical biodiesel production and power cogeneration: technical and economic feasibilities.

    Science.gov (United States)

    Deshpande, A; Anitescu, G; Rice, P A; Tavlarides, L L

    2010-03-01

    An integrated supercritical fluid technology with power cogeneration to produce biodiesel fuels, with no need for the costly separations involved with the conventional technology, is proposed, documented for technical and economic feasibility, and preliminarily designed. The core of the integrated system consists of the transesterification of various triglyceride sources (e.g., vegetable oils and animal fats) with supercritical methanol/ethanol. Part of the reaction products can be combusted by a diesel power generator integrated in the system which, in turn, provides the power needed to pressurize the system and the heat of the exhaust gases necessary in the transesterification step. The latter energy demand can also be satisfied by a fired heater, especially for higher plant capacities. Different versions of this system can be implemented based on the main target of the technology: biodiesel production or diesel engine applications, including power generation. The process options considered for biodiesel fuel production estimate break-even processing costs of biodiesel as low as $0.26/gal ($0.07/L) with a diesel power generator and $0.35/gal ($0.09/L) with a fired heater for a plant capacity of 15,000 gal/day (56,775 L/day). Both are significantly lower than the current processing costs of approximately $0.51/gal ($0.13/L) of biodiesel produced by conventional catalytic methods. A retail cost of biodiesel produced by the proposed method is likely to be competitive with the prices of diesel fuels.

  17. Universal scaling behavior of supercritical matter

    CERN Document Server

    Bolmatov, Dima; Trachenko, K

    2013-01-01

    Properties of supercritical fluids have been of enduring interest since the critical phenomena were discovered by Cagniard de la Tour in 1822, stimulating fundamental theoretical work and development of experimental techniques. Here, we study the thermodynamic properties of the supercritical state, and discover that specific heat shows a crossover between two different dynamic regimes of the low-temperature rigid liquid and high-temperature non-rigid supercritical fluid. We formulate a theory of heat capacity above the crossover, and find good agreement between calculated and experimental data for rare-gas supercritical liquids (Ne, Ar, Kr and Xe) with no free fitting parameters. We derive the relationship between scaling exponents of heat capacity and viscosity in the supercritical region, and show that these exponents exhibit universality. The universality is explained by the universal temperature behavior of the maximal length of the longitudinal phonons that can exist in the supercritical system and that ...

  18. Analysis of gamma irradiated pepper constituents, 3. The supercritical fluid extraction of pepper perfume

    Energy Technology Data Exchange (ETDEWEB)

    Takagi, Kazuko; Okuyama, Tsuneo; Yamauchi, Yoshio; Saito, Muneo.

    1988-11-01

    The extraction of pepper perfume by use of supercritical fluid extraction (SFE) was investigated. Carbon dioxide was used as supercritical mobile phase. SFE was achieved by follow conditions, temperature was 40deg C, pressure was 200 kgf/cm/sup 2/, 5 % methanol was added to mobile phase and the extraction time was 60 minutes. The extracted fraction by this method was yellow oily substance and was pepper perfume rich fraction, while the residue of extraction had not only perfume but also any pungency. And it seems that most part of pepper perfume was extracted by Supercritical fluid extraction. The perfume fraction was analyzed by two way method, that is, supercritical fluid chromatography (SFC) and reversed phase HPLC. SFC conditions were same as SFE. HPLC conditions were described as the first report. By both methods, about 7 peaks were detected. According to their analysis of this fraction, the main component was identified as piperine. On the chromatogram of reversed phase HPLC of extract, most peaks were eluted later than piperine. And it is thought that most perfume components have high hydrophobicity more than piperine. The change of perfume of pepper was able to be discussed based on the extraction by SFE.

  19. Process intensification using CO2 as cosolvent under supercritical conditions applied to the design of biodiesel production

    OpenAIRE

    Maçaira, Jose; Santana, Aline; Oliveira Costa, Ana Carolina; Ramírez, E.; Larrayoz Iriarte, María Angeles

    2014-01-01

    In this work, a new process for biodiesel production under supercritical conditions in presence of cosolvent (CO2) is designed and simulated using the process simulator Aspen Plus. The model was developed using experimental reaction data of continuous catalytic biodiesel synthesis at a 74:25:1 CO2 to methanol to triglycerides molar ratio, temperature range between 150 and 300 C, at 250 bar. To decrease the temperature and pressure of operation and increase the conversion efficiency of biodies...

  20. Direct synthesis of dimethyl carbonate and propylene glycol using potassium bicarbonate as catalyst in supercritical CO2

    OpenAIRE

    Wen Yicun; Zhang Rui; Cang Yu; Zhang Jianchao; Liu Lixiao; Guo Xuhong; Fan Bin

    2015-01-01

    The improved one-pot synthesis of dimethyl carbonate and propylene glycol from propylene oxide, supercritical carbon dioxide, and methanol with potassium bicarbonate as the catalyst has been reported in this paper. As far as we know, it is the first time to use potassium bicarbonate only as the catalyst in the production process which is simple and cheap. Satisfactory conversion rate of propylene oxide and yield of the products could be achieved at the optimized conditions with quite a small ...

  1. Methanol - alternative fuel road traffic

    Energy Technology Data Exchange (ETDEWEB)

    Muendler, H.

    1980-09-01

    This brochure names the fuel properties that are required for road traffic, discusses the replacement of petrol by methanol, discusses the possibilities of manufacturing methanol, draws up a timetable and an organigram for a (M-15) large scale test and compares costs of petrol, methanol, synthesis process petrol and hydrogenation process petrol. Furthermore, the technical requirements of vehicles as well as test results of exhaust gas emissions are also discussed.

  2. Pulsed discharge plasmas in supercritical carbon dioxide

    OpenAIRE

    Kiyan, Tsuyoshi; Uemura, A.; Tanaka, K.; Zhang, C. H.; Namihira, Takao; Sakugawa, Takashi; Katsuki, Sunao; Akiyama, Hidenori; Roy, B.C.; Sasaki, M.; Goto, M.; キヤン, ツヨシ; ナミヒラ, タカオ; サクガワ, タカシ; カツキ, スナオ

    2005-01-01

    In recent years, several studies about electrical discharge plasma in supercritical carbon dioxide (CO2) have been carried out. One of the unique characteristics of supercritical fluid is a large density fluctuation near the critical point that can result in marked dramatic changes of thermal conductivity. Therefore, the electrical discharge plasma produced in supercritical fluid has unique features and reactions unlike those of normal plasma produced in gas phase. In our experiments, two typ...

  3. Stable Amplification and High Current Drop Bistable Switching in Supercritical GaAs Tills

    DEFF Research Database (Denmark)

    Izadpanah, S.H; Jeppsson, B; Jeppesen, Palle

    1974-01-01

    Bistable switching with current drops of 40% and switching times of 100 ps are obtained in pulsed operation of 10¿m supercritically doped n+ nn+ GaAs Transferred Electron Devices (TEDs). When CW-operated the same devices exhibit a 5-17 GHz bandwidth for the stable negative resistance.......Bistable switching with current drops of 40% and switching times of 100 ps are obtained in pulsed operation of 10¿m supercritically doped n+ nn+ GaAs Transferred Electron Devices (TEDs). When CW-operated the same devices exhibit a 5-17 GHz bandwidth for the stable negative resistance....

  4. A study on amphiphilic fluorinated block copolymer in graphite exfoliation using supercritical CO2 for stable graphene dispersion.

    Science.gov (United States)

    Kim, Young Hyun; Lee, Hyang Moo; Choi, Sung Wook; Cheong, In Woo

    2017-09-18

    In this study, poly(2,2,2-trifluoroethyl methacrylate)-block-poly(4-vinylpyridine) (PTFEMA-b-PVP) was synthesized by stepwise reversible addition-fragmentation chain transfer (RAFT) polymerization for the preparation of graphene by the exfoliation of graphite nanoplatelets (GPs) in supercritical CO2 (SCCO2). Two different block copolymers (low and high molecular weights) were prepared with the same block ratio and used at different concentrations in the SCCO2 process. The amount of PTFEMA-b-PVP adsorbed on the GPs and the electrical conductivity of the SCCO2-treated GP samples were evaluated using thermogravimetric analysis (TGA) and four-point probe method, respectively. All GP samples treated with SCCO2 were then dispersed in methanol and the dispersion stability was investigated using online turbidity measurements. The concentration and morphology of few-layer graphene stabilized with PTFEMA-b-PVP in the supernatant solution were investigated by gravimetry, scanning electron microscopy, and Raman spectroscopy. Destabilization study of the graphene dispersions revealed that the longer block copolymer exhibited better affinity for graphene, resulting in a higher yield of stable graphene with minimal defects. Copyright © 2017. Published by Elsevier Inc.

  5. Lipidomics by Supercritical Fluid Chromatography

    Directory of Open Access Journals (Sweden)

    Laurent Laboureur

    2015-06-01

    Full Text Available This review enlightens the role of supercritical fluid chromatography (SFC in the field of lipid analysis. SFC has been popular in the late 1980s and 1990s before almost disappearing due to the commercial success of liquid chromatography (LC. It is only 20 years later that a regain of interest appeared when new commercial instruments were introduced. As SFC is fully compatible with the injection of extracts in pure organic solvent, this technique is perfectly suitable for lipid analysis and can be coupled with either highly universal (UV or evaporative light scattering or highly specific (mass spectrometry detection methods. A short history of the use of supercritical fluids as mobile phase for the separation oflipids will be introduced first. Then, the advantages and drawbacks of SFC are discussed for each class of lipids (fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, prenols, polyketides defined by the LIPID MAPS consortium.

  6. Lipidomics by Supercritical Fluid Chromatography

    Science.gov (United States)

    Laboureur, Laurent; Ollero, Mario; Touboul, David

    2015-01-01

    This review enlightens the role of supercritical fluid chromatography (SFC) in the field of lipid analysis. SFC has been popular in the late 1980s and 1990s before almost disappearing due to the commercial success of liquid chromatography (LC). It is only 20 years later that a regain of interest appeared when new commercial instruments were introduced. As SFC is fully compatible with the injection of extracts in pure organic solvent, this technique is perfectly suitable for lipid analysis and can be coupled with either highly universal (UV or evaporative light scattering) or highly specific (mass spectrometry) detection methods. A short history of the use of supercritical fluids as mobile phase for the separation oflipids will be introduced first. Then, the advantages and drawbacks of SFC are discussed for each class of lipids (fatty acyls, glycerolipids, glycerophospholipids, sphingolipids, sterols, prenols, polyketides) defined by the LIPID MAPS consortium. PMID:26090714

  7. Extraction of essential oil from Pimpinella anisum using supercritical carbon dioxide and comparison with hydrodistillation.

    Science.gov (United States)

    Yamini, Yadollah; Bahramifar, Nader; Sefidkon, Fatemeh; Saharkhiz, Mohamad Jamal; Salamifar, Ehsan

    2008-02-15

    Supercritical fluid extraction (SFE) of essential oil from Pimpinella anisum, using carbon dioxide as a solvent is presented in this work. An orthogonal array design OA9 (3(4)) was applied to select the optimum extraction condition. The effects of pressure, temperature, dynamic extraction time and methanol volume on the extraction efficiency were investigated by the three-level orthogonal array design. Results show that pressure has a significant effect on the extraction efficiency. The extract obtained from P. anisum by using supercritical fluid extraction was compared with the essential oil obtained by hydrodistillation, considering both quantity and quality of the product. SFE products were found to be of markedly different composition, compared with the corresponding hydrodistilated oil. The total amount of extractable substances obtained in SFE (7.5%) is higher than that obtained by hydrodistillation (3.1%) and SFE is faster than hydrodistillation method.

  8. Recuperative supercritical carbon dioxide cycle

    Science.gov (United States)

    Sonwane, Chandrashekhar; Sprouse, Kenneth M; Subbaraman, Ganesan; O'Connor, George M; Johnson, Gregory A

    2014-11-18

    A power plant includes a closed loop, supercritical carbon dioxide system (CLS-CO.sub.2 system). The CLS-CO.sub.2 system includes a turbine-generator and a high temperature recuperator (HTR) that is arranged to receive expanded carbon dioxide from the turbine-generator. The HTR includes a plurality of heat exchangers that define respective heat exchange areas. At least two of the heat exchangers have different heat exchange areas.

  9. Supercritical Fluid Chromatography, Pressurized Liquid Extraction and Supercritical Fluid Extraction

    Energy Technology Data Exchange (ETDEWEB)

    Henry, Matthew C.; Yonker, Clement R.

    2006-06-15

    In this review we examine the related fields of supercritical fluid chromatography (SFC) and supercritical fluid extraction (SFE). We reviewed the published literature in the period from November 2003 to November 2005. Well over 300 papers were published in this period. This large body of work indicates continuing active growth of the field, but an exhaustive review is beyond the scope of this work. We have chosen to include a sampling of publications that best represent the continuing trends and new ideas in the field. In keeping with past reviews on this subject1, we have broadened our scope to include fluid systems operating at high temperature and pressure, but below the critical point. Various terms have been applied to this state: sub-critical fluid extraction, pressurized liquid extraction, and accelerated solvent extraction. The term accelerated solvent extraction has been used by instrument manufacturers to refer to this process, but we will use the more descriptive term pressurized liquid extraction (PLE) to refer to these systems. Most of the research in the field is of an “evolutionary” rather than “revolutionary” nature. As in the previous review period, applications papers make up a majority of the published work. Pharmaceutical applications continue to be a strong theme. Most of the pharmaceutical work has centered on preparative, rather than analytical, separations. Chiral separations are an exception, as analytical scale separations of chiral compounds are an area of intense interest. Food and natural products represent the next largest body of work. Major themes are the isolation and characterization of high-value added foodstuffs, fragrances, and flavor compounds from novel natural materials or agricultural by-products. The areas of food, natural products, and pharmaceutical separation science converge in the area of so-called nutraceuticals. These are typically high-value products, either sold alone or as part of a fortified food, that

  10. Supercritical Water Mixture (SCWM) Experiment

    Science.gov (United States)

    Hicks, Michael C.; Hegde, Uday G.

    2012-01-01

    The subject presentation, entitled, Supercritical Water Mixture (SCWM) Experiment, was presented at the International Space Station (ISS) Increment 33/34 Science Symposium. This presentation provides an overview of an international collaboration between NASA and CNES to study the behavior of a dilute aqueous solution of Na2SO4 (5% w) at near-critical conditions. The Supercritical Water Mixture (SCWM) investigation, serves as important precursor work for subsequent Supercritical Water Oxidation (SCWO) experiments. The SCWM investigation will be performed in DECLICs High Temperature Insert (HTI) for the purpose of studying critical fluid phenomena at high temperatures and pressures. The HTI includes a completely sealed and integrated test cell (i.e., Sample Cell Unit SCU) that will contain approximately 0.3 ml of the aqueous test solution. During the sequence of tests, scheduled to be performed in FY13, temperatures and pressures will be elevated to critical conditions (i.e., Tc = 374C and Pc = 22 MPa) in order to observe salt precipitation, precipitate agglomeration and precipitate transport in the presence of a temperature gradient without the influences of gravitational forces. This presentation provides an overview of the motivation for this work, a description of the DECLIC HTI hardware, the proposed test sequences, and a brief discussion of the scientific research objectives.

  11. Methylnaltrexone bromide methanol monosolvate

    Directory of Open Access Journals (Sweden)

    Xinbo Zhou

    2012-03-01

    Full Text Available In the title compound [systematic name: (4R,4aS,7aR,12bS-3-cyclopropylmethyl-4a,9-hydroxy-7-oxo-2,3,4,4a,5,6,7,7a-octahydro-1H-4,12-methanobenzofuro[3,2-e]isoquinolin-3-ium bromide methanol monosolvate], C21H26NO4+·Br−·CH3OH, two of the three six-membered rings adopt chair conformations while the third, which contains a C=C double bond, adopts an approximate half-boat conformation. The 2,3-dihydrofuran ring adopts an envelope conformation. In the crystal, the components are linked by O—H...O and O—H...Br hydrogen bonds. The absolute stereochemistry was inferred from one of the starting materials.

  12. Methanol synthesis beyond chemical equilibrium

    NARCIS (Netherlands)

    van Bennekom, J. G.; Venderbosch, R. H.; Winkelman, J. G. M.; Wilbers, E.; Assink, D.; Lemmens, K. P. J.; Heeres, H. J.

    2013-01-01

    In commercial methanol production from syngas, the conversion is thermodynamically limited to 0.3-0.7 leading to large recycles of non-converted syngas. This problem can be overcome to a significant extent by in situ condensation of methanol during its synthesis which is possible nowadays due to the

  13. Methanol as an energy carrier

    Energy Technology Data Exchange (ETDEWEB)

    Biedermann, P.; Grube, T.; Hoehlein, B. (eds.)

    2006-07-01

    For the future, a strongly growing energy demand is expected in the transport sector worldwide. Economically efficient oil production will run through a maximum in the next decade. Higher fuel prices and an environmentally desirable reduction of emissions will increase the pressure for reducing fuel consumption and emissions in road traffic. These criteria show the urgent necessity of structural changes in the fuel market. Due to its advantages concerning industrial-scale production, storage and global availability, methanol has the short- to medium-term potential for gaining increased significance as a substitution product in the energy market. Methanol can be produced both from fossil energy sources and from biomass or waste materials through the process steps of synthesis gas generation with subsequent methanol synthesis. Methanol has the potential to be used in an environmentally friendly manner in gasoline/methanol mixtures for flexible fuel vehicles with internal combustion engines and in diesel engines with pure methanol. Furthermore, it can be used in fuel cell vehicles with on-board hydrogen production in direct methanol fuel cell drives, and in stationary systems for electricity and heat generation as well as for hydrogen production. Finally, in portable applications it serves as an energy carrier for electric power generation. In this book, the processes for the production and use of methanol are presented and evaluated, markets and future options are discussed and issues of safety and environmental impacts are addressed by a team of well-known authors. (orig.)

  14. Analysis of antioxidants extracted from polypropylene by supercritical fluid extraction.

    Science.gov (United States)

    Garde, J A; Catalá, R; Gavara, R

    1998-01-01

    Maximal potential migration of six antioxidants (AO) from five polypropylene (PP) formulations was determined by two supercritical fluid extraction (SFE) procedures, both of which contained static and dynamic steps. All analytical conditions affecting the extraction were studied and optimized using Irgafos 168 as standard. SFE was more efficient as temperature and fluid density increased. During the static step in which the samples were exposed to the fluid without flux, the introduction of hexane and methanol as fluid modifiers significantly improved the extraction. Hexane appears to facilitate polymer swelling while methanol solvates the antioxidants. In the dynamic step (in which the extraction actually occurs) time is the key parameter. Extraction for 90 min results in an efficiency of around 75%. The introduction of modifiers during this step (by an HPLC-SFE procedure) did not produce any significant improvement. When SFE was carried out on all samples, extraction efficiency was around 75% except for Irganox 1010 and Hostanox O3. The large molecular volume of these antioxidants may be responsible for the considerable reduction of extraction efficiency. Particle size and shape of polymer sample were also important. The greater the surface to volume ratio the greater the extraction efficiency.

  15. A comparative study using HPLC and packed column supercritical fluid chromatography for the assay of three anti-psychotic dosage forms.

    Science.gov (United States)

    Patela, Y P; Dhorda, U J; Sundaresan, M

    1998-11-01

    A reproducible and selective method was developed for the analysis of three anti-pschycotics, i.e. haloperidol, trifluoperazine and trihexyphenidyl in bulk and dosage forms using packed column supercritical fluid chromatography (SFC). The analytes were resolved by elution with supercritical fluid carbon dioxide doped with 16.67% (v/v) methanol containing 0.8% isopropylamine. Parallel studies were performed by HPLC using ion pairing reagent and a comparison is discussed. The method was successfully used for the assay of three formulations containing a combination of: (1) haloperidol-trihexyphenidyl; (2) haloperidol-trifluoperazine; (3) trifluoperazine-trihexyphenidyl.

  16. INTEGRATED SUPERCRITICAL FLUID EXTRACTION AND BIOPROCESSING

    Directory of Open Access Journals (Sweden)

    Owen Catchpole

    2012-01-01

    Full Text Available Supercritical fluids are increasingly being used and promoted at a laboratory and pilot scale to produce high value, natural bioactives from biologically based raw materials. Supercritical CO2 is overwhelmingly the solvent of choice for these operations, but is largely limited to the processing of dry raw materials and the extraction of low polarity, low molecular weight compounds. The use of co-solvents and the use of alternative ‘near-critical’ extraction fluids such as dimethyl ether show potential to mitigate these limitations. Commercialisation of new supercritical extraction processes has arguably been limited because the supercritical extraction process has been developed in isolation of other processing steps necessary to achieve a successful product. This study reviews recent developments in integrated processing that incorporate the use of supercritical fluids for bioseparations and in particular process schemes that produce high value natural bioactives. Integrated processes include prior operation (fermentation, extraction, enzyme pre-treatment, physical fractionation or size reduction followed by supercritical extraction or fractionation and processes in which operations are carried out in situ in supercritical fluids (supercritical chromatography, enzymatic conversion, precipitation and coating of solutes. The use of co-solvents and alternative extraction solvents in these processes is discussed. Prospects for future developments are also discussed.

  17. Effects of Lanthanide Ions on Electrooxidation of Methanol

    Institute of Scientific and Technical Information of China (English)

    WANG Hai-tao; YIN Yu-chun; GAO Shu-juan

    2008-01-01

    Four kinds of lanthanide ions(Sm3+,Yb3+,Eu3+,La3+) as an additive were added into the aqueous solution containing methanol,respectively,and their effects on methanol elecotrooxidation in aqueous solutions were studied with cyclic voltammetry.The results show that the four kinds of ions have promotion action upon the electrooxidation of methanol to different degrees.The best additive,Sm3+,can increase the anodic oxidation current of methanol by 80% and the peak potential shifted negatively about 50 mV.The promotion effects of the lanthanide ions were considered to be related to the extranuclear electron distribution of these ions and their adsorption on the Pt electrode surface.

  18. Supercritical water oxidation - Microgravity solids separation

    Science.gov (United States)

    Killilea, William R.; Hong, Glenn T.; Swallow, Kathleen C.; Thomason, Terry B.

    1988-01-01

    This paper discusses the application of supercritical water oxidation (SCWO) waste treatment and water recycling technology to the problem of waste disposal in-long term manned space missions. As inorganic constituents present in the waste are not soluble in supercritical water, they must be removed from the organic-free supercritical fluid reactor effluent. Supercritical water reactor/solids separator designs capable of removing precipitated solids from the process' supercritical fluid in zero- and low- gravity environments are developed and evaluated. Preliminary experiments are then conducted to test the concepts. Feed materials for the experiments are urine, feces, and wipes with the addition of reverse osmosis brine, the rejected portion of processed hygiene water. The solid properties and their influence on the design of several oxidation-reactor/solids-separator configurations under study are presented.

  19. [Study on condition for extraction of arctiin from fruits of Arctium lappa using supercritical fluid extraction].

    Science.gov (United States)

    Dong, Wen-hong; Liu, Ben

    2006-08-01

    To study the feasibility of supercritical fluid extraction (SFE) for arctiin from the fruits of Arctium lappa. The extracts were analyzed by HPLC, optimum extraction conditions were studied by orthogonal tests. The optimal extraction conditions were: pressure 40 MPa, temperature 70 degrees C, using methanol as modifier carrier at the rate of 0.55 mL x min(-1), static extraction time 5 min, dynamic extraction 30 min, flow rate of CO2 2 L x min(-1). SFE has the superiority of adjustable polarity, and has the ability of extracting arctiin.

  20. Valorization of horse manure through catalytic supercritical water gasification.

    Science.gov (United States)

    Nanda, Sonil; Dalai, Ajay K; Gökalp, Iskender; Kozinski, Janusz A

    2016-06-01

    The organic wastes such as lignocellulosic biomass, municipal solid waste, sewage sludge and livestock manure have attracted attention as alternative sources of energy. Cattle manure, a waste generated in surplus amounts from the feedlot, has always been a chief environmental concern. This study is focused on identifying the candidacy of horse manure as a next generation feedstock for biofuel production through supercritical water gasification. The horse manure was gasified in supercritical water to examine the effects of temperature (400-600°C), biomass-to-water ratio (1:5 and 1:10) and reaction time (15-45min) at a pressure range of 23-25MPa. The horse manure and resulting biochar were characterized through carbon-hydrogen-nitrogen-sulfur (CHNS), inductively coupled plasma-mass spectrometry (ICP-MS), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy and scanning electron microscopy (SEM). The effects of alkali catalysts such as NaOH, Na2CO3 and K2CO3 at variable concentrations (1-2wt%) were investigated to maximize the hydrogen yields. Supercritical water gasification of horse manure with 2wt% Na2CO3 at 600°C and 1:10 biomass-to-water ratio for 45min revealed maximum hydrogen yields (5.31mmol/g), total gas yields (20.8mmol/g) with greater carbon conversion efficiency (43.1%) and enhanced lower heating value of gas products (2920kJ/Nm(3)). The manure-derived biochars generated at temperatures higher than 500°C also demonstrated higher thermal stability (weight loss 70wt%) suggesting their application in enhancing soil fertility and carbon sequestration. The results propose that supercritical water gasification could be a proficient remediation technology for horse manure to generate hydrogen-rich gas products.

  1. Mechanisms and kinetics of noncatalytic ether reaction in supercritical water. 2. Proton-transferred fragmentation of dimethyl ether to formaldehyde in competition with hydrolysis.

    Science.gov (United States)

    Nagai, Yasuharu; Matubayasi, Nobuyuki; Nakahara, Masaru

    2005-04-28

    Noncatalytic reaction pathways and rates of dimethyl ether (DME) in supercritical water are determined in a tube reactor made of quartz according to liquid- and gas-phase 1H and 13C NMR observations. The reaction is studied at two concentrations (0.1 and 0.5 M) in supercritical water at 400 degrees C and over a water-density range of 0.1-0.6 g/cm3. The supercritical water reaction is compared with the neat one (in the absence of solvent) at 0.1 M and 400 degrees C. DME is found to decompose through (i) the proton-transferred fragmentation to methane and formaldehyde and (ii) the hydrolysis to methanol. Formaldehyde from reaction (i) is consecutively subjected to four types of redox reactions. Two of them proceed even without solvent: (iii) the unimolecular proton-transferred decarbonylation forming hydrogen and carbon monoxide and (iv) the bimolecular self-disproportionation generating methanol and carbon monoxide. When the solvent water is present, two additional paths are open: (v) the bimolecular self-disproportionation of formaldehyde with reactant water, producing methanol and formic acid, and (vi) the bimolecular cross-disproportionation between formaldehyde and formic acid, yielding methanol and carbonic acid. Methanol is produced through the three types of disproportionations (iv)-(vi) as well as the hydrolysis (ii). The presence of solvent water decelerates the proton-transferred fragmentation of DME; the rate constant is reduced by 40% at 0.5 g/cm3. This is caused by the suppression of low-frequency concerted motion corresponding to the reaction coordinate for the simultaneous C-O bond scission and proton transfer from one methyl carbon to the other. In contrast to the proton-transferred fragmentation, the hydrolysis of DME is markedly accelerated by increasing the water density. The latter becomes more important than the former in supercritical water at densities greater than 0.5 g/cm3.

  2. Towards Overhauser DNP in supercritical CO2

    Science.gov (United States)

    van Meerten, S. G. J.; Tayler, M. C. D.; Kentgens, A. P. M.; van Bentum, P. J. M.

    2016-06-01

    Overhauser Dynamic Nuclear Polarization (ODNP) is a well known technique to improve NMR sensitivity in the liquid state, where the large polarization of an electron spin is transferred to a nucleus of interest by cross-relaxation. The efficiency of the Overhauser mechanism for dipolar interactions depends critically on fast local translational dynamics at the timescale of the inverse electron Larmor frequency. The maximum polarization enhancement that can be achieved for 1H at high magnetic fields benefits from a low viscosity solvent. In this paper we investigate the option to use supercritical CO2 as a solvent for Overhauser DNP. We have investigated the diffusion constants and longitudinal nuclear relaxation rates of toluene in high pressure CO2. The change in 1H T1 by addition of TEMPO radical was analyzed to determine the Overhauser cross-relaxation in such a mixture, and is compared with calculations based on the Force Free Hard Sphere (FFHS) model. By analyzing the relaxation data within this model we find translational correlation times in the range of 2-4 ps, depending on temperature, pressure and toluene concentration. Such short correlation times may be instrumental for future Overhauser DNP applications at high magnetic fields, as are commonly used in NMR. Preliminary DNP experiments have been performed at 3.4 T on high pressure superheated water and model systems such as toluene in high pressure CO2.

  3. Towards Overhauser DNP in supercritical CO2.

    Science.gov (United States)

    van Meerten, S G J; Tayler, M C D; Kentgens, A P M; van Bentum, P J M

    2016-06-01

    Overhauser Dynamic Nuclear Polarization (ODNP) is a well known technique to improve NMR sensitivity in the liquid state, where the large polarization of an electron spin is transferred to a nucleus of interest by cross-relaxation. The efficiency of the Overhauser mechanism for dipolar interactions depends critically on fast local translational dynamics at the timescale of the inverse electron Larmor frequency. The maximum polarization enhancement that can be achieved for (1)H at high magnetic fields benefits from a low viscosity solvent. In this paper we investigate the option to use supercritical CO2 as a solvent for Overhauser DNP. We have investigated the diffusion constants and longitudinal nuclear relaxation rates of toluene in high pressure CO2. The change in (1)H T1 by addition of TEMPO radical was analyzed to determine the Overhauser cross-relaxation in such a mixture, and is compared with calculations based on the Force Free Hard Sphere (FFHS) model. By analyzing the relaxation data within this model we find translational correlation times in the range of 2-4ps, depending on temperature, pressure and toluene concentration. Such short correlation times may be instrumental for future Overhauser DNP applications at high magnetic fields, as are commonly used in NMR. Preliminary DNP experiments have been performed at 3.4T on high pressure superheated water and model systems such as toluene in high pressure CO2.

  4. Studies of methanol maser rings

    CERN Document Server

    Bartkiewicz, A; van Langevelde, H J; De Buizer, J M; Pihlström, Y

    2011-01-01

    We present the results of studies of a new class of 6.7 GHz methanol maser sources with a ring-like emission structure discovered recently with the EVN. We have used the VLA to search for water masers at 22 GHz and radio continuum at 8.4 GHz towards a sample of high-mass star forming regions showing a ring-like distribution of methanol maser spots. Using the Gemini telescopes we found mid-infrared (MIR) counterparts of five methanol rings with a resolution of 0."15. The centres of methanol maser rings are located within, typically, only 0."2 of the MIR emission peak, implying their physical relation with a central star. These results strongly support a scenario wherein the ring-like structures appear at the very early stage of massive star formation before either water-maser outflows or H II regions are seen.

  5. [Supercritical CO2 fluid extraction of Rosmarinus officinalis and capability of extracts eliminate OH radical].

    Science.gov (United States)

    Zhang, Chong; Li, Jia-Cheng; Zhang, De-La; Feng, Yu-Hong; Zhang, Ya-Nan; Chen, Si-Li

    2008-05-01

    Supercritical CO2 fluid extraction process of antioxidation active components from Rosmarinus officinalis was studied. A new extraction process of components extracted from R. officinalis by supercritical CO2 fluid extraction (SFE-CO2 ) was studied in detail. The capability of that the extract eliminate *OH radical was tested by electron paramagnetic resonance (EPR) technique and spin catch technique. With free radical clearance as index, by range and variance analysis, the optimum extraction process conditions were: keeping pressure at 30 MPa and temperature at 75 degrees C for 1 h, in the same time adding alcohol 0.30 mL x g(-1).

  6. Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

    Science.gov (United States)

    Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

    2010-03-25

    A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

  7. Accidental methanol ingestion: Case report

    Directory of Open Access Journals (Sweden)

    Bakker Jan

    2010-02-01

    Full Text Available Abstract Background The incidence of methanol (CH3OH intoxication differs enormously from country to country. Methanol intoxication is extremely rare in the Dutch population. Even a low dose can already be potentially lethal. Patients are conventionally treated with hemodialysis. Therefore we'd like to present a report of a foreign sailor in Rotterdam who accidentally caused himself severe methanol intoxication, with a maximum measured concentration of 4.4 g/L. Case presentation The patient presented with hemodynamic instability and severe metabolic acidosis with pH 6.69. The anion gap was 39 mmol/L and the osmol gap 73 mosmol/kg. Treatment with ethanol and continuous venovenous hemodiafiltration (CVVH-DF was initiated. Despite the hemodynamic instability it is was possible to achieve rapid correction of pH and methanol concentration with CVVH-DF while maintaining a stable and therapeutic ethanol serum concentration. Despite hemodynamic and acid-base improvement, our patient developed massive cerebral edema leading to brain death. Permission for organ donation was unfortunately not ascertained. Conclusions We conclude that in a hemodynamic instable situation high methanol concentrations and methanol-induced derangements of homeostasis are safely and effectively treated with CVVH-DF and that severe cerebral edema is another possible cause of death rather than the classical bleeding in the putamen area.

  8. Acute methanol toxicity in minipigs

    Energy Technology Data Exchange (ETDEWEB)

    Dorman, D.C.; Dye, J.A.; Nassise, M.P.; Ekuta, J.; Bolon, B.

    1993-01-01

    The pig has been proposed as a potential animal model for methanol-induced neuro-ocular toxicosis in humans because of its low liver tetrahydrofolate levels and slower rate of formate metabolism compared to those of humans. To examine the validity of this animal model, 12 4-month-old female minipigs (minipig YU) were given a single oral dose of water or methanol at 1.0, 2.5, or 5.0 g/kg body wt by gavage (n = 3 pigs/dose). Dose-dependent signs of acute methanol intoxication, which included mild CNS depression, tremors, ataxia, and recumbency, developed within 0.5 to 2.0 hr, and resolved by 52 hr. Methanol- and formate-dosed pigs did not develop optic nerve lesions, toxicologically significant formate accumulation, or metabolic acidosis. Based on results following a single dose, female minipigs do not appear to be overtly sensitive to methanol and thus may not be a suitable animal model for acute methanol-induced neuroocular toxicosis.

  9. Fixed Bed Adsorption of Drugs on Silica Aerogel from Supercritical Carbon Dioxide Solutions

    Directory of Open Access Journals (Sweden)

    Giuseppe Caputo

    2013-01-01

    Full Text Available Supercritical adsorption coupled with the high adsorption capacity of silica aerogel allows the preparation of a new kind of delivery systems of poor water soluble drugs. In order to overcome drawbacks of conventional techniques where the use of liquid solvents can cause the fracture of aerogel porous structure, in this work a new adsorption process of drugs from a supercritical mixture is proposed. Adsorption takes place from a fluid solution of the drug in supercritical CO2 and ethanol as cosolvent. A fixed bed adsorption plant has been developed to allow fast mixing of fluid phase and effective contact in the adsorption column. The use of ethanol as cosolvent allows to overcome the limitation of supercritical adsorption due to low solubility of many drugs in supercritical CO2. Adsorption isotherms were measured for one-model substance, nimesulide, at 40°C, and breakthrough curve was experimentally obtained. The drug loading of the drug into silica aerogel was up to 9 wt%. The drug composite was characterized using scanning electron microscopy, and release kinetics of the adsorbed drug were also evaluated by in vitro dissolution tests. The dissolution of nimesulide from loaded aerogel is much faster than dissolution of crystalline nimesulide. Around 80% of nimesulide dissolves from the aerogel within 6 minutes, whereas dissolving 80% of the crystalline drug takes about 90 min.

  10. Using supercritical fluids to refine hydrocarbons

    Science.gov (United States)

    Yarbro, Stephen Lee

    2015-06-09

    A system and method for reactively refining hydrocarbons, such as heavy oils with API gravities of less than 20 degrees and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure, using a selected fluid at supercritical conditions. A reaction portion of the system and method delivers lightweight, volatile hydrocarbons to an associated contacting unit which operates in mixed subcritical/supercritical or supercritical modes. Using thermal diffusion, multiphase contact, or a momentum generating pressure gradient, the contacting unit separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques.

  11. Water extractable arabinoxylan aerogels prepared by supercritical CO2 drying.

    Science.gov (United States)

    Marquez-Escalante, Jorge; Carvajal-Millan, Elizabeth; Miki-Yoshida, Mario; Alvarez-Contreras, Lorena; Toledo-Guillén, Alma Rosa; Lizardi-Mendoza, Jaime; Rascón-Chu, Agustín

    2013-05-14

    Water extractable arabinoxylan (WEAX) aerogels were prepared by extracting the solvent from the alcogels (WEAX hydrogels with an alcohol as the solvent) with carbon dioxide under supercritical conditions. WEAX aerogels were characterized using scanning electron microscopy and adsorption and desorption nitrogen isotherms. The micrographs indicate a heterogeneous porous network structure in WEAX aerogel. Adsorption/desorption nitrogen isotherms of this material were type IV, which confirm that this material possess a mesoporous structure. WEAX aerogels rehydration capability was evaluated and the water absorption mechanism was determined. The WEAX aerogels water absorption mechanism was non-Fickian (n = 0.54).

  12. Water Extractable Arabinoxylan Aerogels Prepared by Supercritical CO2 Drying

    Directory of Open Access Journals (Sweden)

    Agustín Rascón-Chu

    2013-05-01

    Full Text Available Water extractable arabinoxylan (WEAX aerogels were prepared by extracting the solvent from the alcogels (WEAX hydrogels with an alcohol as the solvent with carbon dioxide under supercritical conditions. WEAX aerogels were characterized using scanning electron microscopy and adsorption and desorption nitrogen isotherms. The micrographs indicate a heterogeneous porous network structure in WEAX aerogel. Adsorption/desorption nitrogen isotherms of this material were type IV, which confirm that this material possess a mesoporous structure. WEAX aerogels rehydration capability was evaluated and the water absorption mechanism was determined. The WEAX aerogels water absorption mechanism was non-Fickian (n = 0.54.

  13. Synthesis of a proline-modified acrylic acid copolymer in supercritical CO2 for glass-ionomer dental cement applications.

    Science.gov (United States)

    Moshaverinia, Alireza; Roohpour, Nima; Darr, Jawwad A; Rehman, Ihtesham U

    2009-06-01

    Supercritical (sc-) fluids (such as sc-CO(2)) represent interesting media for the synthesis of polymers in dental and biomedical applications. Sc-CO(2) has several advantages for polymerization reactions in comparison to conventional organic solvents. It has several advantages in comparison to conventional polymerization solvents, such as enhanced kinetics, being less harmful to the environment and simplified solvent removal process. In our previous work, we synthesized poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone) (PAA-IA-NVP) terpolymers in a supercritical CO(2)/methanol mixture for applications in glass-ionomer dental cements. In this study, proline-containing acrylic acid copolymers were synthesized, in a supercritical CO(2) mixture or in water. Subsequently, the synthesized polymers were used in commercially available glass-ionomer cement formulations (Fuji IX commercial GIC). Mechanical strength (compressive strength (CS), diametral tensile strength (DTS) and biaxial flexural strength (BFS)) and handling properties (working and setting time) of the resulting modified cements were evaluated. It was found that the polymerization reaction in an sc-CO(2)/methanol mixture was significantly faster than the corresponding polymerization reaction in water and the purification procedures were simpler for the former. Furthermore, glass-ionomer cement samples made from the terpolymer prepared in sc-CO(2)/methanol exhibited higher CS and DTS and comparable BFS compared to the same polymer synthesized in water. The working properties of glass-ionomer formulations made in sc-CO(2)/methanol were comparable and better than the values of those for polymers synthesized in water.

  14. Combined supercritical fluid extraction/solid-phase extraction with octadecylsilane cartridges as a sample preparation technique for the ultratrace analysis of a drug metabolite in plasma.

    Science.gov (United States)

    Liu, H; Cooper, L M; Raynie, D E; Pinkston, J D; Wehmeyer, K R

    1992-04-01

    Supercritical fluid extraction was coupled with solid-phase extraction using octadecylsilane cartridges for the selective isolation of ultratrace levels of a drug metabolite, mebeverine alcohol, from plasma. Plasma was directly applied to the extraction cartridge, the cartridge was washed to remove protein and then extracted under supercritical conditions using CO2/5% methanol. The effluent from the extraction cell was bubbled through a small volume of 2-propanol to trap the extracted mebeverine alcohol. The effects of extraction pressure and temperature on analyte recovery were examined. The absolute recovery, selectivity, precision, and accuracy of the combined supercritical fluid extraction/solid-phase extraction approach were compared to those of conventional solid-phase extraction using gas chromatography/mass spectrometry in the selected-ion monitoring mode. Mebeverine alcohol was used as a model compound, and dog plasma was employed as the biological matrix for these studies.

  15. Polarization and spectral shift of benzophenone in supercritical water.

    Science.gov (United States)

    Fonseca, T L; Georg, H C; Coutinho, K; Canuto, S

    2009-04-30

    Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense pi-pi* transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and

  16. Unusual case of methanol poisoning

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, L.; Henderson, M. (St. James' s Univ. Hospital, Leeds (United Kingdom). Dept. of Chemical Pathology); Madi, S.; Mellor, L. (St. James' s Univ. Hospital, Leeds (United Kingdom). Dept. of Medicine, and Pharmacy)

    1993-01-09

    A 31-year-old man with a history of alcohol abuse presented to the accident and emergency department complaining of blurred vision. 4 h previously he had drunk 300 mL de-icer fluid. Electrolytes, urea, creatinine, glucose, and blood-gas analysis were normal. Measured osmolality, however, was 368 mosmol/kg with a calculated osmolality of 300 mosmol/kg, which indicated a greatly increased osmolar gap. He was therefore given 150 mL whisky and admitted. Methanol was later reported as 200 mg/dL. Ethylene glycol was not detected, but another glycol, propylene glycol, was present at 47 mg/dL. 10 h after ingestion an intravenous infusion of ethanol was started and he was hemodialysed for 7 h. After dialysis he was given a further 100 mL whisky and the rate of ethanol infusion was reduced to 11 g per h. Methanol and ethanol were measured twice daily until methanol was under 10/mg/dL: The recommendation is that blood ethanol be maintained between 100 and 200 mg/dL during treatment of methanol poisoning. This concentration was not achieved, presumably because of the high rate of ethanol metabolism often found in alcoholics. Antifreeze solutions commonly contain methanol and ethylene glycol. Sometimes propylene glycol is substituted because it has properties similar to those of ethylene glycol but is less toxic. The authors postulate that propylene glycol inhibited the metabolism of methanol in the patient, thus sparing him from the toxic effects of methanol.

  17. Recent progress in supercritical fluid science for biofuel production from woody biomass

    Institute of Scientific and Technical Information of China (English)

    Shiro Saka

    2006-01-01

    Owing to an environment-friendly utilization of resources, increased attention has been focused on fuels and chemicals from biomass as an alternative to fossil resources. In addition, supercritical fluid technology has been considered to be an environmentally-benign treatment. Therefore, its technology was applied for a conversion of biomass to useful fuels and chemicals in order to mitigate environmental loading. For example, supercritical water treatment has demonstrated that lignocellulosics can be hydrolyzed to become lignin-derived products for useful aromatic chemicals and carbohydrate-derived products, such as polysaccharides,oligosaccharides and monosaccharides of glucose, mannose and xylose used for subsequent ethanol fermentation. If this treatment is prolonged, lignocellulosics were found to be converted to organic acids such as formic, acetic, glycolic and lactic acids which can be converted to methane for biofuel. When alcohols, such as methanol and ethanol, were used instead of water, some other useful products were achieved, and its liquefied products were found to have a potential for liquid biofuel. In this study, therefore, our research achievements in supercritical fluid science of woody biomass will be introduced for clean and green chemistry for a sustainable environment.

  18. The Supercritical Pile Model for GRBs

    Science.gov (United States)

    Kazanas, Demos

    2006-01-01

    We present the spectral and temporal radiative signatures expected within the Supercritical Pile model of Gamma Ray Bursts (GRB). This model is motivated by the need for a process that provides the dissipation necessary in GRB and presents a well defined scheme for converting the energy stored in the relativistic protons of the Relativistic Blast Waves (RBW) associated with GRB into radiation; at the same time it leads to spectra which exhibit a peak in the burst nuF(sub nu) distribution at an energy E(sub p) approximately equal to 1 MeV in the observer s frame, in agreement with observation and largely independent of the Lorentz factor GAMMA of the associated relativistic outflow. Furthermore, this scheme does not require (but does not preclude) acceleration of particles at the shock other than that provided by the isotropization of the flow bulk kinetic energy on the RBW frame. In the present paper we model in detail the evolution of protons, electrons and photons from a RBW to produce detailed spectra of the prompt GRB phase as a function of time from across a very broad range spanning roughly 4 log10 GAMMA decades in frequency. The model spectra are in general agreement with observations and provide a means for the delineating of the model parameters through direct comparison with trends observed in GRB properties.

  19. Oxy-combustor operable with supercritical fluid

    Energy Technology Data Exchange (ETDEWEB)

    Brun, Klaus; McClung, Aaron M.; Owston, Rebecca A.

    2017-04-04

    An oxy-combustor is provided which comprises a combustion vessel including at least one solid fuel slurry inlet port, at least one oxygen inlet port and at least one supercritical fluid inlet port, wherein the combustion vessel is operable at an operating pressure of at least 1,100 psi; an interior of the combustion vessel comprises a combustion chamber and a supercritical fluid infusion chamber surrounding at least a part of the combustion chamber, the supercritical fluid infusion chamber and the combustion chamber are separated by a porous liner surrounding the combustion chamber, and the supercritical infusion chamber is located between the porous liner and an outer casing of the combustion vessel.

  20. Evaluation of scale-up from analytical to preparative supercritical fluid chromatography.

    Science.gov (United States)

    Enmark, Martin; Åsberg, Dennis; Leek, Hanna; Öhlén, Kristina; Klarqvist, Magnus; Samuelsson, Jörgen; Fornstedt, Torgny

    2015-12-18

    An approach for reliable transfer from analytical to preparative scale supercritical fluid chromatography was evaluated. Here, we accounted for the conditions inside the columns as well as to the fact that most analytical instruments are volume-controlled while most preparative scale units are mass-controlled. The latter is a particular problem when performing pilot scale experiments and optimizations prior to scaling up to production scale. This was solved by measuring the mass flow, the pressure and the temperature on the analytical unit using external sensors. Thereafter, it was revealed with a design of experiments approach that the methanol fraction and the pressure are the two most important parameters to control for preserved retention throughout the scale-up; for preserved selectivity the temperature was most important in this particular system. Using this approach, the resulting chromatograms from the preparative unit agreed well with those from the analytical unit while keeping the same column length and particles size. A brief investigation on how the solute elution volume varies with the volumetric flow rate revealed a complex dependency on pressure, density and apparent methanol content. Since the methanol content is a parameter of great importance to control during the scale up, we must be careful when changing operational and column design conditions which generates deviations in pressure, density and methanol content between different columns. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. The Pore Structure of Direct Methanol Fuel Cell Electrodes

    DEFF Research Database (Denmark)

    Lund, Peter Brilner

    2005-01-01

    The pore structure and morphology of direct methanol fuel cell electrodes are characterized using mercury intrusion porosimetry and scanning electron microscopy. It is found that the pore size distributions of printed primer and catalyst layers are largely dictated by the powders used to make the...

  2. A first-principles study of Pt–Ni bimetallic cluster adsorption on the anatase TiO{sub 2} (1 0 1) surface: Probing electron effect of Ni in TiO{sub 2} (1 0 1)-bimetallic cluster (Pt–Ni) on the adsorption and dissociation of methanol

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Feila, E-mail: liufeila@u.washington.edu [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195 (United States); Xiao, Peng, E-mail: xiaopeng@cqu.edu.cn [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Uchaker, Evan, E-mail: uchaker@u.washington.edu [Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195 (United States); He, Huichao, E-mail: hehuichao985@gmail.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Zhou, Ming, E-mail: Zhoumingcqu2007@163.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China); Zhou, Xin, E-mail: zhoux@hit.edu.cn [State Key Laboratory of Urban Water Resource and Environment, Institute of Theoretical and Simulation Chemistry, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology, Harbin 150080 (China); Zhang, Yunhuai, E-mail: xp2031@163.com [College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China)

    2014-10-01

    Graphical abstract: - Highlights: • Condensed Fukui function is used to predict the regioselectivity of clusters. • Pt–Ni alloy and TiO{sub 2} can effectively oxidize methanol compared with pure Pt. • The methanol dehydrogenation over Pt{sub 3}Ni/TiO{sub 2} is an optimal reaction pathway. • The alloying of Ni can effectively alleviate CO poisoning. - Abstract: A density functional theory (DFT) based method in conjunction with the projector augmented wave and pseudopotential methods have been applied to investigate the adsorption of Pt{sub 4} and Pt{sub 3}Ni on the anatase TiO{sub 2} (1 0 1) surface. Two stable Pt{sub 3}Ni adsorptions with considerable adsorption energies on the anatase TiO{sub 2} (1 0 1) surface were identified. Analysis of the partial density (PDOS) of states and Bader charge suggest that the electronic structure of Pt is modified by Ni due to the electron transfer from Ni to Pt atoms in the Pt{sub 3}Ni clusters. The 2cO (3cO)-PtNi-5cTi conformation of the adsorbed Pt{sub 3}Ni on the anatase TiO{sub 2} (1 0 1) surface provides a more feasible model for electron injection through the Pt{sub 3}Ni/TiO{sub 2} interface. The reactivity of Pt{sub 3}Ni/TiO{sub 2} is superior to Pt{sub 4}/TiO{sub 2} and effectively manifests itself in the eased decomposition of O-H bonds derived by methanol and alleviative CO adsorption.

  3. An electrode with Ni(II) loaded analcime zeolite catalyst for the electrooxidation of methanol

    Institute of Scientific and Technical Information of China (English)

    Seyed Naser Azizi; Shahram Ghasemi; Neda Salek Gilani

    2014-01-01

    There is a high overvoltage in the oxidation of methanol in fuel cells, and so modified electrodes are used to decrease it. A modified electrode that used Ni(II) loaded analcime zeolite to catalyze the electrooxidation of methanol in alkaline solution was proposed. Analcime zeolite was synthesized by hydrothermal synthesis, and Ni(II) ions were incorporated into the analcime structure, which was then mixed with carbon paste to prepare modified electrode. The electrocatalytic oxidation of methanol on the surface of the modified electrode in alkaline solution was investigated by cyclic voltammetry and chronoamperometry. The effects of the scan rate of the potential, concentration of methanol, and amount of zeolite were investigated. The rate constant for the catalytic reaction of methanol was 6 × 103 cm3 mol-1 s-1 from measurements using chronoamperometry. The proposed electrode significantly improved the electron transfer rate and decreased the overpotential for methanol oxidation.

  4. Determination of solvation kinetics in supercritical fluids

    Energy Technology Data Exchange (ETDEWEB)

    Bright, F.V.

    1993-01-01

    Objective was to study solvation processes in pure and entrainer-modified supercritical fluids. Specific topics were: Kinetics for solvation in supercritical media, influence on entrainers on solvation, reversibility of solvation, effects of solvation on intramolecular solute-solute interaction kinetics, and impact of fluid density on these processes. Time-resolved fluorescence spectroscopy was used as the main analytical tool. A summary is given of the 2.5 years' research.

  5. Charting the landscape of supercritical string theory.

    Science.gov (United States)

    Hellerman, Simeon; Swanson, Ian

    2007-10-26

    Special solutions of string theory in supercritical dimensions can interpolate in time between theories with different numbers of spacetime dimensions and different amounts of world sheet supersymmetry. These solutions connect supercritical string theories to the more familiar string duality web in ten dimensions and provide a precise link between supersymmetric and purely bosonic string theories. Dimension quenching and c duality appear to be natural concepts in string theory, giving rise to large networks of interconnected theories.

  6. Water in supercritical carbon dioxide dyeing

    Directory of Open Access Journals (Sweden)

    Zheng Lai-Jiu

    2015-01-01

    Full Text Available This paper investigates the effect of water serving as entrainer on the dyeing of wool fabrics in supercritical carbon dioxide. Compared with previous supercritical dyeing methods, addition of water makes the dyeing process more effective under low temperature and low pressure. During dyeing process, dyestuff can be uniformly distributed on fabrics’s surface due to water interaction, as a result coloration is enhanced while color difference is decreased.

  7. Determination of arsenic species in solid matrices utilizing supercritical fluid extraction coupled with gas chromatography after derivatization with thioglycolic acid n-butyl ester.

    Science.gov (United States)

    Wang, Zhifeng; Cui, Zhaojie

    2016-12-01

    A method using derivatization and supercritical fluid extraction coupled with gas chromatography was developed for the analysis of dimethylarsinate, monomethylarsonate and inorganic arsenic simultaneously in solid matrices. Thioglycolic acid n-butyl ester was used as a novel derivatizing reagent. A systematic discussion was made to investigate the effects of pressure, temperature, flow rate of the supercritical CO2 , extraction time, concentration of the modifier, and microemulsion on extraction efficiency. The application for real environmental samples was also studied. Results showed that thioglycolic acid n-butyl ester was an effective derivatizing reagent that could be applied for arsenic speciation. Using methanol as modifier of the supercritical CO2 can raise the extraction efficiency, which can be further enhanced by adding a microemulsion that contains Triton X-405. The optimum extraction conditions were: 25 MPa, 90°C, static extraction for 10 min, dynamic extraction for 25 min with a flow rate of 2.0 mL/min of supercritical CO2 modified by 5% v/v methanol and microemulsion. The detection limits of dimethylarsinate, monomethylarsonate, and inorganic arsenic in solid matrices were 0.12, 0.26, and 1.1 mg/kg, respectively. The optimized method was sensitive, convenient, and reliable for the extraction and analysis of different arsenic species in solid samples.

  8. Atypical Particle Heating at a Supercritical Interplanetary Shock

    Science.gov (United States)

    Wilson, Lynn B., III

    2010-01-01

    We present the first observations at an interplanetary shock of large amplitude (> 100 mV/m pk-pk) solitary waves and large amplitude (approx.30 mV/m pk-pk) waves exhibiting characteristics consistent with electron Bernstein waves. The Bernstein-like waves show enhanced power at integer and half-integer harmonics of the cyclotron frequency with a broadened power spectrum at higher frequencies, consistent with the electron cyclotron drift instability. The Bernstein-like waves are obliquely polarized with respect to the magnetic field but parallel to the shock normal direction. Strong particle heating is observed in both the electrons and ions. The observed heating and waveforms are likely due to instabilities driven by the free energy provided by reflected ions at this supercritical interplanetary shock. These results offer new insights into collisionless shock dissipation and wave-particle interactions in the solar wind.

  9. Supercritical fluid reverse micelle separation

    Science.gov (United States)

    Fulton, John L.; Smith, Richard D.

    1993-01-01

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W.sub.o that determines the maximum size of the reverse micelles. The maximum ratio W.sub.o of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions.

  10. Supercritical fluid reverse micelle separation

    Science.gov (United States)

    Fulton, J.L.; Smith, R.D.

    1993-11-30

    A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

  11. One Step Preparation of Controlled Drug Release Systems in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    CAO Liqin; WANG Chengwei; CHEN Liuping

    2009-01-01

    Drug delivery systems based on copolymers of N-isopropylacrylamide were fn-st prepared by a one step method, in which supercritical carbon dioxide was simultaneously used as a polymerization medium and an impregnation agent. The obtained microspheres were characterized by scanning electronic microscopy (SEM), differential scan-ning calorimetry (DSC), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The release effect of the in situ prepared microgels impregnated with ibuprofen was presented through in vitro release simulation.

  12. Competitive Solvation of the Imidazolium Cation by Water and Methanol

    CERN Document Server

    Chaban, Vitaly

    2014-01-01

    Imidazolium-based ionic liquids are widely used in conjunction with molecular liquids for various applications. Solvation, miscibility and similar properties are of fundamental importance for successful implementation of theoretical schemes. This work reports competitive solvation of the 1,3-dimethylimidazolium cation by water and methanol. Employing molecular dynamics simulations powered by semiempirical Hamiltonian (electronic structure level of description), the local structure nearly imidazolium cation is described in terms of radial distribution functions. Although water and methanol are chemically similar, water appears systematically more successful in solvating the 1,3-dimethylimidazolium cation. This result fosters construction of future applications of the ternary ion-molecular systems.

  13. Scaledown of a methanol reactor

    Energy Technology Data Exchange (ETDEWEB)

    Berty, J.M.

    1983-07-01

    This article shows how it is possible to define operating conditions for pilot plants and development labs by scaling down a commercial reactor. Points out that scaledown consideration and experiment planning can be done in a similar manner for the boiling water-cooled, Lurgi-type reactor. Explains that although the design of large, single-train plants to produce methanol for fuel use has different economic objectives, product specifications, and technical constraints from the traditional commercial methanol plants, the same fundamental laws of thermodynamics and reaction kinetics apply to both types of operation.

  14. Selective Synthesis of Manganese/Silicon Complexes in Supercritical Water

    Directory of Open Access Journals (Sweden)

    Jiancheng Wang

    2014-01-01

    Full Text Available A series of manganese salts (Mn(NO32, MnCl2, MnSO4, and Mn(Ac2 and silicon materials (silica sand, silica sol, and tetraethyl orthosilicate were used to synthesize Mn/Si complexes in supercritical water using a tube reactor. X-ray diffraction (XRD, X-ray photoelectron spectrometer (XPS, transmission electron microscopy (TEM, and scanning electron microscopy (SEM were employed to characterize the structure and morphology of the solid products. It was found that MnO2, Mn2O3, and Mn2SiO4 could be obtained in supercritical water at 673 K in 5 minutes. The roles of both anions of manganese salts and silicon species in the formation of manganese silicon complexes were discussed. The inorganic manganese salt with the oxyacid radical could be easily decomposed to produce MnO2/SiO2 and Mn2O3/SiO2. It is interesting to found that Mn(Ac2 can react with various types of silicon to produce Mn2SiO4. The hydroxyl groups of the SiO2 surface from different silicon sources enhance the reactivity of SiO2.

  15. Numerical simulation of the solvate structures of acetylsalicylic acid in supercritical carbon dioxide containing polar co-solvents

    Science.gov (United States)

    Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.; Kumeev, R. S.; Golubev, V. A.

    2016-07-01

    Hydrogen-bonded complexes of acetylsalicylic acid with polar co-solvents in supercritical carbon dioxide, modified by methanol, ethanol, and acetone of 0.03 mole fraction concentration, are studied by numerical methods of classical molecular dynamics simulation and quantum chemical calculations. The structure, energy of formation, and lifetime of hydrogen-bonded complexes are determined, along with their temperature dependences (from 318 to 388 K at constant density of 0.7 g cm-3). It is shown that the hydrogen bonds between acetylsalicylic acid and methanol are most stable at 318 K and are characterized by the highest value of absolute energy. At higher supercritical temperatures, however, the longest lifetime is observed for acetylsalicylic acid-ethanol complexes. These results correlate with the known literature experimental data showing that the maximum solubility of acetylsalicylic acid at density values close to those considered in this work and at temperatures of 318 and 328 K is achieved when using methanol and ethanol as co-solvents, respectively.

  16. Ultraviolet and Visible Photochemistry of Methanol at 3D Mesoporous Networks: TiO2 and Au-TiO2

    Science.gov (United States)

    2013-05-23

    aerogel, while Au−TiO2 aerogel remains highly active for methanol photooxidation. The wavelength dependence of formate production on Au−TiO2 tracks the...under acetone into a supercritical dryer (Fisons Bio-Rad E3100). The gels were rinsed with liquid CO2 before taking the liquid CO2 above its critical... methanol as the test reactant because it is a common product of the oxidation of more complex species56 yet is simple enough structurally that its

  17. High-performance hybrid oxide catalyst of manganese and cobalt for low-pressure methanol synthesis

    National Research Council Canada - National Science Library

    Li, Cheng-Shiuan; Melaet, Gérôme; Ralston, Walter T; An, Kwangjin; Brooks, Christopher; Ye, Yifan; Liu, Yi-Sheng; Zhu, Junfa; Guo, Jinghua; Alayoglu, Selim; Somorjai, Gabor A

    2015-01-01

    ... in the scanning transmission electron microscopy mode. Through control experiments, we find that the catalyst's chemical nature and architecture are the key factors in enabling the enhanced methanol synthesis and ethylene production...

  18. Supercritical Extraction of Lycopene from Tomato Industrial Wastes with Ethane

    OpenAIRE

    Mendes, Rui L.; Cristino, Ana F.; Nobre, Beatriz P.; Luisa Gouveia; António F. Palavra; Patricia G. S. Matos

    2012-01-01

    Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO2...

  19. Supercritical Extraction of Lycopene from Tomato Industrial Waste with Ethane

    OpenAIRE

    Nobre, Beatriz P.; Gouveia, L.; Patricia G. S. Matos; Cristino, Ana F.; António F. Palavra; Mendes, Rui L.

    2012-01-01

    Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO2 and a near critical mixture of ethane and p...

  20. Crystal doping aided by rapid expansion of supercritical solutions.

    Science.gov (United States)

    Vemavarapu, Chandra; Mollan, Matthew J; Needham, Thomas E

    2002-01-01

    The purpose of this study was to test the utility of rapid expansion of supercritical solution (RESS) based cocrystallizations in inducing polymorph conversion and crystal disruption of chlorpropamide (CPD). CPD crystals were recrystallized by the RESS process utilizing supercritical carbon dioxide as the solvent. The supercritical region investigated for solute extraction ranged from 45 to 100 degrees C and 2000 to 8000 psi. While pure solute recrystallization formed stage I of these studies, stage II involved recrystallization of CPD in the presence of urea (model impurity). The composition, morphology, and crystallinity of the particles thus produced were characterized utilizing techniques such as microscopy, thermal analysis, x-ray powder diffractometry, and high-performance liquid chromatography. Also, comparative evaluation between RESS and evaporative crystallization from liquid solvents was performed. RESS recrystallizations of commercially available CPD (form A) resulted in polymorph conversion to metastable forms C and V, depending on the temperature and pressure of the recrystallizing solvent. Cocrystallization studies revealed the formation of eutectic mixtures and solid solutions of CPD + urea. Formation of the solid solutions resulted in the crystal disruption of CPD and subsequent amorphous conversion at urea levels higher than 40% wt/wt. Consistent with these results were the reductions in melting point (up to 9 degrees C) and in the DeltaH(f) values of CPD (up to 50%). Scanning electron microscopy revealed a particle size reduction of up to an order of magnitude upon RESS processing. Unlike RESS, recrystallizations from liquid organic solvents lacked the ability to affect polymorphic conversions. Also, the incorporation of urea into the lattice of CPD was found to be inadequate. In providing the ability to control both the particle and crystal morphologies of active pharmaceutical ingredients, RESS proved potentially advantageous to crystal

  1. Drying of supercritical carbon dioxide with membrane processes

    NARCIS (Netherlands)

    Lohaus, Theresa; Scholz, Marco; Koziara, Beata T.; Benes, N.E.; Wessling, Matthias

    2015-01-01

    In supercritical extraction processes regenerating the supercritical fluid represents the main cost constraint. Membrane technology has potential for cost efficient regeneration of water-loaded supercritical carbon dioxide. In this study we have designed membrane-based processes to dehydrate water-l

  2. Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol

    DEFF Research Database (Denmark)

    Alberico, E.; Nielsen, Martin

    2015-01-01

    The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous...

  3. X-ray photodesorption from methanol ice

    Science.gov (United States)

    Andrade, D. P. P.; Rocco, M. L. M.; Boechat-Roberty, H. M.

    2010-12-01

    The abundances of molecules and ions depend on the mechanisms of their formation and destruction that can occur both in the gas phase and in the condensed phase on grain surfaces. Photodesorption of grain surface species may explain the relative high abundances of gaseous neutral or ionic species detected in cold environments. X-ray photons from young stars are able to penetrate cold and dense regions inside protoplanetary discs, leading to molecular dissociation and desorption of photo-products from icy molecules on grain mantles. This paper aims to experimentally investigate the contribution of ion desorption from methanol ice stimulated by soft X-rays for producing chemically active ions in protoplanetary discs. The measurements were carried out at the Brazilian synchrotron light source (LNLS), using X-ray photons at the methanol O1s resonance energy (537 eV). Some possible pathways for the H- and O- formation from singly charged desorbed ions are suggested. The photodesorption yields for positive and negative ions were determined and compared with previous results obtained using different ionization agents, such as electrons, heavy ions and photons at different energies. We also correlate our results to the ion production in protoplanetary discs.

  4. Advanced Supercritical Carbon Dioxide Brayton Cycle Development

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Mark [Univ. of Wisconsin, Madison, WI (United States); Sienicki, James [Argonne National Lab. (ANL), Argonne, IL (United States); Moisseytsev, Anton [Argonne National Lab. (ANL), Argonne, IL (United States); Nellis, Gregory [Univ. of Wisconsin, Madison, WI (United States); Klein, Sanford [Univ. of Wisconsin, Madison, WI (United States)

    2015-10-21

    Fluids operating in the supercritical state have promising characteristics for future high efficiency power cycles. In order to develop power cycles using supercritical fluids, it is necessary to understand the flow characteristics of fluids under both supercritical and two-phase conditions. In this study, a Computational Fluid Dynamic (CFD) methodology was developed for supercritical fluids flowing through complex geometries. A real fluid property module was implemented to provide properties for different supercritical fluids. However, in each simulation case, there is only one species of fluid. As a result, the fluid property module provides properties for either supercritical CO2 (S-CO2) or supercritical water (SCW). The Homogeneous Equilibrium Model (HEM) was employed to model the two-phase flow. HEM assumes two phases have same velocity, pressure, and temperature, making it only applicable for the dilute dispersed two-phase flow situation. Three example geometries, including orifices, labyrinth seals, and valves, were used to validate this methodology with experimental data. For the first geometry, S-CO2 and SCW flowing through orifices were simulated and compared with experimental data. The maximum difference between the mass flow rate predictions and experimental measurements is less than 5%. This is a significant improvement as previous works can only guarantee 10% error. In this research, several efforts were made to help this improvement. First, an accurate real fluid module was used to provide properties. Second, the upstream condition was determined by pressure and density, which determines supercritical states more precise than using pressure and temperature. For the second geometry, the flow through labyrinth seals was studied. After a successful validation, parametric studies were performed to study geometric effects on the leakage rate. Based on these parametric studies, an optimum design strategy for the see

  5. Design of experiments for enantiomeric separation in supercritical fluid chromatography.

    Science.gov (United States)

    Landagaray, Elodie; Vaccher, Claude; Yous, Saïd; Lipka, Emmanuelle

    2016-02-20

    A new chiral melatoninergic ligand, potentially successor of Valdoxan(®), presenting an improved pharmacological profile with regard to agomelatine, was chosen as a probe for a supercritical fluid chromatographic separation carried-out on an amylose tris[(S)-1-α-methylbenzylcarbamate] based stationary phase. The goal of this work was to optimize simultaneously three factors identified to have a significant influence to obtain the best resolution in the shortest analysis time (i.e., retention time of the second eluting enantiomer) for this chiral compound. For this purpose a central circumscribed composite (CCC) design was developed with three factors: the flow-rate, the pressure outlet and the percentage of ethanol to optimize of two responses: shortest analysis time and best resolution. The optimal conditions obtained via the optimizer mode of the software (using the Nelder-Mead method) i.e., CO2/EtOH 86:14 (v:v), 104bar, 3.2mLmin(-1) at 35°C lead to a resolution of 3.27 in less than 6min. These conditions were transposed to a preparative scale where a concentrated methanolic solution of 40mM was injected with a sample loop of 100μL. This step allowed to separate an amount of around 65mg of racemic melatonin ligand in only 3h with impressive yields (97%) and enantiomeric excess (99.5%).

  6. Biodegradation of Tetrachlorothylene Using Methanol as Co-metabolic Substrate

    Institute of Scientific and Technical Information of China (English)

    QI YANG; HAI-TAO SHANG; HUI-DI LI; HONG-BO XI; JIAN-LONG WANG

    2008-01-01

    Objective To investigate the biodegradation of tetrachloroethylene(PCE using methanol as electron donor by acclimated anaerobic sludge.Methods HP-6890 gas chromatograph(GC),together with HP-7694 autosampler,was used to analyze the concentration of PCE and intermediates. Results PCE could be decholrinated reductively to DCE via TCE,and probably further to VC and ethylene.The degradation of PCE and TCE conformed to first-order reaction kinetics.The reaction rate constants were 0.8991 d-1and 0.068 d-1,respectively,and the corresponding half-life were 0.77d and 10.19 d,respectively.TCE production rate constant was 0.1333 d-1.showing that PCE was degraded more rapidly than TCE. Conclusion Methanol is an electron donor suitable for PCE degradation and the cometabolic electron donors are not limiting factors for PCE degradation.

  7. Pharmaceutical applications of supercritical carbon dioxide.

    Science.gov (United States)

    Kaiser, C S; Römpp, H; Schmidt, P C

    2001-12-01

    The appearance of a supercritical state was already observed at the beginning of the 19th century. Nevertheless, the industrial extraction of plant and other natural materials started about twenty years ago with the decaffeination of coffee. Today carbon dioxide is the most common gas for supercritical fluid extraction in food and pharmaceutical industry. Since pure supercritical carbon dioxide is a lipophilic solvent, mixtures with organic solvents, especially alcohols, are used to increase the polarity of the extraction fluid; more polar compounds can be extracted in this way. The main fields of interest are the extraction of vegetable oils from plant material in analytical and preparative scale, the preparation of essential oils for food and cosmetic industry and the isolation of substances of pharmaceutical relevance. Progress in research was made by the precise measurement of phase equilibria data by means of different methods. Apart from extraction, supercritical fluid chromatography was introduced in the field of analytics, as well as micro- and nanoparticle formation using supercritical fluids as solvent or antisolvent. This review presents pharmaceutical relevant literature of the last twenty years with special emphasis on extraction of natural materials.

  8. Characteristics of compressible flow of supercritical kerosene

    Institute of Scientific and Technical Information of China (English)

    Feng-Quan Zhong; Xue-Jun Fan; Jing Wang; Gong Yu; Jian-Guo Li

    2012-01-01

    In this paper,compressible flow of aviation kerosene at supercritical conditions has been studied both numerically and experimentally.The thermophysical properties of supercritical kerosene are calculated using a 10-species surrogate based on the principle of extended corresponding states (ECS).Isentropic acceleration of supercritical kerosene to subsonic and supersonic speeds has been analyzed numerically.It has been found that the isentropic relationships of supercritical kerosene are significantly different from those of ideal gases.A two-stage fuel heating and delivery system is used to heat the kerosene up to a temperature of 820 K and pressure of 5.5 MPa with a maximum mass flow rate of 100 g/s.The characteristics of supercritical kerosene flows in a converging-diverging nozzle (Laval nozzle) have been studied experimentally.The results show that stable supersonic flows of kerosene could be established in the temperature range of 730 K-820 K and the measurements in the wall pressure agree with the numerical calculation.

  9. Corrosion in Supercritical carbon Dioxide: Materials, Environmental Purity, Surface Treatments, and Flow Issues

    Energy Technology Data Exchange (ETDEWEB)

    Sridharan, Kumar; Anderson, Mark

    2013-12-10

    separately to high purity CO{sub 2}. Task 3: Evaluation of surface treatments on the corrosion performance of alloys in supercritical CO{sub 2}: Surface treatments can be very beneficial in improving corrosion resistance. Shot peening and yttrium and aluminum surface treatments will be investigated. Shot peening refines the surface grain sizes and promotes protective Cr-oxide layer formation. Both yttrium and aluminum form highly stable oxide layers (Y{sub 2}O{sub 3} and Al{sub 2}O{sub 3}), which can get incorporated in the growing Fe-oxide layer to form an impervious complex oxide to enhance corrosion resistance. Task 4: Study of flow-assisted corrosion of select alloys in supercritical CO{sub 2} under a selected set of test conditions: To study the effects of flow-assisted corrosion, tests will be conducted in a supercritical CO{sub 2} flow loop. An existing facility used for supercritical water flow studies at the proposing university will be modified for use in this task. The system is capable of flow velocities up to 10 m/s and can operate at temperatures and pressures of up to 650°C and 20 MPa, respectively. All above tasks will be performed in conjunction with detailed materials characterization and analysis using scanning electron microscopy/energy dispersive spectroscopy (SEM-EDS), x-ray diffraction (XRD), Auger electron spectroscopy (AES) techniques, and weight change measurements. Inlet and outlet gas compositions will be monitored using gas chromatography-mass spectrometry (GCMS).

  10. Enhanced methanol utilization in direct methanol fuel cell

    Science.gov (United States)

    Ren, Xiaoming; Gottesfeld, Shimshon

    2001-10-02

    The fuel utilization of a direct methanol fuel cell is enhanced for improved cell efficiency. Distribution plates at the anode and cathode of the fuel cell are configured to distribute reactants vertically and laterally uniformly over a catalyzed membrane surface of the fuel cell. A conductive sheet between the anode distribution plate and the anodic membrane surface forms a mass transport barrier to the methanol fuel that is large relative to a mass transport barrier for a gaseous hydrogen fuel cell. In a preferred embodiment, the distribution plate is a perforated corrugated sheet. The mass transport barrier may be conveniently increased by increasing the thickness of an anode conductive sheet adjacent the membrane surface of the fuel cell.

  11. Fermentation of methanol in the sheep rumen.

    OpenAIRE

    Pol, A.; Demeyer, D. I.

    1988-01-01

    Sheep fed a hay-concentrate diet were adapted to pectin administration and ruminal infusion of methanol. Both treatments resulted in a strong increase in the rate of methanogenesis from methanol. Quantitative data show that methanol was exclusively converted into methane. Treatments did not influence ruminal volatile fatty acid percentages.

  12. The fate of methanol in anaerobic bioreactors

    NARCIS (Netherlands)

    Florencio, L.

    1994-01-01

    Methanol is an important component of certain industrial wastewaters. In anaerobic environments, methanol can be utilized by methanogens and acetogens. In wastewater treatment plants, the conversion of methanol into methane is preferred because this conversion is responsible for chemical

  13. The fate of methanol in anaerobic bioreactors.

    NARCIS (Netherlands)

    Florencio, L.

    1994-01-01

    Methanol is an important component of certain industrial wastewaters. In anaerobic environments, methanol can be utilized by methanogens and acetogens. In wastewater treatment plants, the conversion of methanol into methane is preferred because this conversion is responsible for chemical oxygen dema

  14. Development of an Accelerated Methodology to Study Degradation of Materials in Supercritical Water for Application in High Temperature Power Plants

    Science.gov (United States)

    Rodriguez, David

    The decreasing supply of fossil fuel sources, coupled with the increasing concentration of green house gases has placed enormous pressure to maximize the efficiency of power generation. Increasing the outlet temperature of these power plants will result in an increase in operating efficiency. By employing supercritical water as the coolant in thermal power plants (nuclear reactors and coal power plants), the plant efficiency can be increased to 50%, compared to traditional reactors which currently operate at 33%. The goal of this dissertation is to establish techniques to characterize the mechanical properties and corrosion behavior of materials exposed to supercritical water. Traditionally, these tests have been long term exposure tests spanning months. The specific goal of this dissertation is to develop a methodology for accelerated estimation of corrosion rates in supercritical water that can be sued as a screening tool to select materials for long term testing. In this study, traditional methods were used to understand the degradation of materials in supercritical water and establish a point of comparison to the first electrochemical studies performed in supercritical water. Materials studied included austenitic steels (stainless steel 304, stainless steel 316 and Nitronic 50) and nickel based alloys (Inconel 625 and 718). Surface chemistry of the oxide layer was characterized using scanning electron microscopy, X-ray diffraction, FT-IR, Raman and X-ray photoelectron spectroscopies. Stainless steel 304 was subjected to constant tensile load creep tests in water at a pressure of 27 MPa and at temperatures of 200 °C, 315 °C and supercritical water at 450 °C for 24 hours. It was determined that the creep rate for stainless steel 304 exposed to supercritical water would be unacceptable for use in service. It was observed that the formation of hematite was favored in subcritical temperatures, while magnetite was formed in the supercritical region. Corrosion of

  15. Enhancing power cycle efficiency for a supercritical Brayton cycle power system using tunable supercritical gas mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Wright, Steven A.; Pickard, Paul S.; Vernon, Milton E.; Radel, Ross F.

    2017-08-29

    Various technologies pertaining to tuning composition of a fluid mixture in a supercritical Brayton cycle power generation system are described herein. Compounds, such as Alkanes, are selectively added or removed from an operating fluid of the supercritical Brayton cycle power generation system to cause the critical temperature of the fluid to move up or down, depending upon environmental conditions. As efficiency of the supercritical Brayton cycle power generation system is substantially optimized when heat is rejected near the critical temperature of the fluid, dynamically modifying the critical temperature of the fluid based upon sensed environmental conditions improves efficiency of such a system.

  16. Driving Interconnected Networks to Supercriticality

    Directory of Open Access Journals (Sweden)

    Filippo Radicchi

    2014-04-01

    Full Text Available Networks in the real world do not exist as isolated entities, but they are often part of more complicated structures composed of many interconnected network layers. Recent studies have shown that such mutual dependence makes real networked systems potentially exposed to atypical structural and dynamical behaviors, and thus there is an urgent necessity to better understand the mechanisms at the basis of these anomalies. Previous research has mainly focused on the emergence of atypical properties in relation to the moments of the intra- and interlayer degree distributions. In this paper, we show that an additional ingredient plays a fundamental role for the possible scenario that an interconnected network can face: the correlation between intra- and interlayer degrees. For sufficiently high amounts of correlation, an interconnected network can be tuned, by varying the moments of the intra- and interlayer degree distributions, in distinct topological and dynamical regimes. When instead the correlation between intra- and interlayer degrees is lower than a critical value, the system enters in a supercritical regime where dynamical and topological phases are no longer distinguishable.

  17. Supercritical fluid extraction of hops

    Directory of Open Access Journals (Sweden)

    ZORAN ZEKOVIC

    2007-01-01

    Full Text Available Five cultivars of hop were extracted by the method of supercritical fluid extraction using carbon dioxide (SFE–CO2 as extractant. The extraction (50 g of hop sample using a CO2 flow rate of 97.725 L/h was done in the two steps: 1. extraction at 150 bar and 40°C for 2.5 h (sample of series A was obtained and, after that, the same sample of hop was extracted in the second step: 2. extraction at 300 bar and 40 °C for 2.5 h (sample of series B was obtained. The Magnum cultivar was chosen for the investigation of the extraction kinetics. For the qualitative and quantitative analysis of the obtained hop extracts, the GC-MS method was used. Two of four themost common compounds of hop aroma (a-humulene and b-caryophyllene were detected in samples of series A. In addition, isomerized a-acids and a high content of b-acids were detected. The a-acids content in the samples of series B was the highest in the extract of the Magnum cultivar (it is a bitter variety of hop. The low contents of a-acids in all the other hop samples resulted in extracts with low a-acids content, i.e., that contents were under the prescribed a-acids content.

  18. Supercritical carbon dioxide hop extraction

    Directory of Open Access Journals (Sweden)

    Pfaf-Šovljanski Ivana I.

    2005-01-01

    Full Text Available The hop of Magnum cultivar was extracted using supercritical carbon dioxide (SFE-as extractant. Extraction was carried out in the two steps: the first one being carried out at 150 bar and 40°C for 2.5 h (Extract A, and the second was the extraction of the same hop sample at 300 bar and 40°C for 2.5 h (Extract B. Extraction kinetics of the system hop-SFE-CO2 was investigated. Two of four most common compounds of hop aroma (α-humulene and β-caryophyllene were detected in Extract A. Isomerised α-acids and β-acids were detected too. a-Acid content in Extract B was high (that means it is a bitter variety of hop. Mathematical modeling using empirical model characteristic time model and simple single sphere model has been performed on Magnum cultivar extraction experimental results. Characteristic time model equations, best fitted experimental results. Empirical model equation, fitted results well, while simple single sphere model equation poorly approximated the results.

  19. Supercritical waste oxidation pump investigation

    Energy Technology Data Exchange (ETDEWEB)

    Thurston, G.; Garcia, K.

    1993-02-01

    This report investigates the pumping techniques and pumping equipment that would be appropriate for a 5,000 gallon per day supercritical water oxidation waste disposal facility. The pumps must boost water, waste, and additives from atmospheric pressure to approximately 27.6 MPa (4,000 psia). The required flow ranges from 10 gpm to less than 0.1 gpm. For the higher flows, many commercial piston pumps are available. These pumps have packing and check-valves that will require periodic maintenance; probably at 2 to 6 month intervals. Several commercial diaphragm pumps were also discovered that could pump the higher flow rates. Diaphragm pumps have the advantage of not requiring dynamic seals. For the lower flows associated with the waste and additive materials, commercial diaphragm pumps. are available. Difficult to pump materials that are sticky, radioactive, or contain solids, could be injected with an accumulator using an inert gas as the driving mechanism. The information presented in this report serves as a spring board for trade studies and the development of equipment specifications.

  20. Direct synthesis of dimethyl carbonate and propylene glycol using potassium bicarbonate as catalyst in supercritical CO2

    Directory of Open Access Journals (Sweden)

    Wen Yicun

    2015-03-01

    Full Text Available The improved one-pot synthesis of dimethyl carbonate and propylene glycol from propylene oxide, supercritical carbon dioxide, and methanol with potassium bicarbonate as the catalyst has been reported in this paper. As far as we know, it is the first time to use potassium bicarbonate only as the catalyst in the production process which is simple and cheap. Satisfactory conversion rate of propylene oxide and yield of the products could be achieved at the optimized conditions with quite a small amount of by-products. Our new method offers an attractive choice for the production of dimethyl carbonate in large-scale industry efficiently and environmental friendly.

  1. Hydrodynamics and Mass Transfer Performance in Supercritical Fluid Extraction Columns

    Institute of Scientific and Technical Information of China (English)

    石冰洁; 张泽廷; 等

    2002-01-01

    New models for describing hydrodynamics and mass transfer performance in supercritical fluid extraction columns were proposed.Those models were proved by experimental data,which were obtained in supercritical fluid extraction packed column,spray column and sieve tray column respectively.The inner diameter of those columns areΦ25mm,These experimental systems include supercritical carbon dioxideisopropanol-water and supercritical carbon dioxide-ethanol-water,in which supercritical carbon dioxide was dispersed phase,and another was continuous phase.The extraction processes were operated with continuous countercurrent flow.The predicted values are agreed well with experimental data.

  2. DNS of High Pressure Supercritical Combustion

    Science.gov (United States)

    Chong, Shao Teng; Raman, Venkatramanan

    2016-11-01

    Supercritical flows have always been important to rocket motors, and more recently to aircraft engines and stationary gas turbines. The purpose of the present study is to understand effects of differential diffusion on reacting scalars using supercritical isotropic turbulence. Focus is on fuel and oxidant reacting in the transcritical region where density, heat capacity and transport properties are highly sensitive to variations in temperature and pressure. Reynolds and Damkohler number vary as a result and although it is common to neglect differential diffusion effects if Re is sufficiently large, this large variation in temperature with heat release can accentuate molecular transport differences. Direct numerical simulations (DNS) for one step chemistry reaction between fuel and oxidizer are used to examine the differential diffusion effects. A key issue investigated in this paper is if the flamelet progress variable approach, where the Lewis number is usually assumed to be unity and constant for all species, can be accurately applied to simulate supercritical combustion.

  3. Supercritical fluid thermodynamics for coal processing

    Energy Technology Data Exchange (ETDEWEB)

    van Swol, F. (Illinois Univ., Urbana, IL (United States). Dept. of Chemical Engineering); Eckert, C.A. (Georgia Inst. of Tech., Atlanta, GA (United States). School of Chemical Engineering)

    1988-09-15

    The main objective of this research is to develop an equation of state that can be used to predict solubilities and tailor supercritical fluid solvents for the extraction and processing of coal. To meet this objective we have implemented a two-sided. approach. First, we expanded the database of model coal compound solubilities in higher temperature fluids, polar fluids, and fluid mixtures systems. Second, the unique solute/solute, solute/cosolvent and solute/solvent intermolecular interactions in supercritical fluid solutions were investigated using spectroscopic techniques. These results increased our understanding of the molecular phenomena that affect solubility in supercritical fluids and were significant in the development of an equation of state that accurately reflects the true molecular makeup of the solution. (VC)

  4. Supercritical fluid mixing in Diesel Engine Applications

    Science.gov (United States)

    Bravo, Luis; Ma, Peter; Kurman, Matthew; Tess, Michael; Ihme, Matthias; Kweon, Chol-Bum

    2014-11-01

    A numerical framework for simulating supercritical fluids mixing with large density ratios is presented in the context of diesel sprays. Accurate modeling of real fluid effects on the fuel air mixture formation process is critical in characterizing engine combustion. Recent work (Dahms, 2013) has suggested that liquid fuel enters the chamber in a transcritical state and rapidly evolves to supercritical regime where the interface transitions from a distinct liquid/gas interface into a continuous turbulent mixing layer. In this work, the Peng Robinson EoS is invoked as the real fluid model due to an acceptable compromise between accuracy and computational tractability. Measurements at supercritical conditions are reported from the Constant Pressure Flow (CPF) chamber facility at the Army Research Laboratory. Mie and Schlieren optical spray diagnostics are utilized to provide time resolved liquid and vapor penetration length measurement. The quantitative comparison presented is discussed. Oak Ridge Associated Universities (ORAU).

  5. Heat Transfer Phenomena of Supercritical Fluids

    Energy Technology Data Exchange (ETDEWEB)

    Krau, Carmen Isabella; Kuhn, Dietmar; Schulenberg, Thomas [Forschungszentrum Karlsruhe, Institute for Nuclear and Energy Technologies, 76021 Karlsruhe (Germany)

    2008-07-01

    In concepts for supercritical water cooled reactors, the reactor core is cooled and moderated by water at supercritical pressures. The significant temperature dependence of the fluid properties of water requires an exact knowledge of the heat transfer mechanism to avoid fuel pin damages. Near the pseudo-critical point a deterioration of heat transfer might happen. Processes, that take place in this case, are not fully understood and are due to be examined systematically. In this paper a general overview on the properties of supercritical water is given, experimental observations of different authors will be reviewed in order to identify heat transfer phenomena and onset of occurrence. The conceptional design of a test rig to investigate heat transfer in the boundary layer will be discussed. Both, water and carbon dioxide, may serve as operating fluids. The loop, including instrumentation and safety devices, is shown and suitable measuring methods are described. (authors)

  6. Recovery of cobalt from spent lithium-ion batteries using supercritical carbon dioxide extraction.

    Science.gov (United States)

    Bertuol, Daniel A; Machado, Caroline M; Silva, Mariana L; Calgaro, Camila O; Dotto, Guilherme L; Tanabe, Eduardo H

    2016-05-01

    Continuing technological development decreases the useful lifetime of electronic equipment, resulting in the generation of waste and the need for new and more efficient recycling processes. The objective of this work is to study the effectiveness of supercritical fluids for the leaching of cobalt contained in lithium-ion batteries (LIBs). For comparative purposes, leaching tests are performed with supercritical CO2 and co-solvents, as well as under conventional conditions. In both cases, sulfuric acid and H2O2 are used as reagents. The solution obtained from the supercritical leaching is processed using electrowinning in order to recover the cobalt. The results show that at atmospheric pressure, cobalt leaching is favored by increasing the amount of H2O2 (from 0 to 8% v/v). The use of supercritical conditions enable extraction of more than 95wt% of the cobalt, with reduction of the reaction time from 60min (the time employed in leaching at atmospheric pressure) to 5min, and a reduction in the concentration of H2O2 required from 8 to 4% (v/v). Electrowinning using a leach solution achieve a current efficiency of 96% and a deposit with cobalt concentration of 99.5wt%.

  7. Accelerated Stress Corrosion Crack Initiation of Alloys 600 and 690 in Hydrogenated Supercritical Water

    Science.gov (United States)

    Moss, Tyler; Was, Gary S.

    2017-04-01

    The objective of this study is to determine whether stress corrosion crack initiation of Alloys 600 and 690 occurs by the same mechanism in subcritical and supercritical water. Tensile bars of Alloys 690 and 600 were strained in constant extension rate tensile experiments in hydrogenated subcritical and supercritical water from 593 K to 723 K (320 °C to 450 °C), and the crack initiation behavior was characterized by high-resolution electron microscopy. Intergranular cracking was observed across the entire temperature range, and the morphology, structure, composition, and temperature dependence of initiated cracks in Alloy 690 were consistent between hydrogenated subcritical and supercritical water. Crack initiation of Alloy 600 followed an Arrhenius relationship and did not exhibit a discontinuity or change in slope after crossing the critical temperature. The measured activation energy was 121 ± 13 kJ/mol. Stress corrosion crack initiation in Alloy 690 was fit with a single activation energy of 92 ± 12 kJ/mol across the entire temperature range. Cracks were observed to propagate along grain boundaries adjacent to chromium-depleted metal, with Cr2O3 observed ahead of crack tips. All measures of the SCC behavior indicate that the mechanism for stress corrosion crack initiation of Alloy 600 and Alloy 690 is consistent between hydrogenated subcritical and supercritical water.

  8. Liposomes Size Engineering by Combination of Ethanol Injection and Supercritical Processing.

    Science.gov (United States)

    Santo, Islane Espirito; Campardelli, Roberta; Albuquerque, Elaine Cabral; Vieira De Melo, Silvio A B; Reverchon, Ernesto; Della Porta, Giovanna

    2015-11-01

    Supercritical fluid extraction using a high-pressure packed tower is proposed not only to remove the ethanol residue from liposome suspensions but also to affect their size and distribution leading the production of nanosomes. Different operating pressures, temperatures, and gas to liquid ratios were explored and ethanol was successfully extracted up to a value of 400 ppm; liposome size and distribution were also reduced by the supercritical processing preserving their integrity, as confirmed by Z-potential data and Trasmission Electron Microscopy observations. Operating at 120 bar and 38°C, nanosomes with a mean diameter of about 180 ± 40 nm and good storage stability were obtained. The supercritical processing did not interfere on drug encapsulation, and no loss of entrapped drug was observed when the water-soluble fluorescein was loaded as a model compound. Fluorescein encapsulation efficiency was 30% if pure water was used during the supercritical extraction as processing fluid; whereas an encapsulation efficiency of 90% was obtained if the liposome suspension was processed in water/fluorescein solution. The described technology is easy to scale up to an industrial production and merge in one step the solvent extraction, liposome size engineering, and an excellent drug encapsulation in a single operation unit.

  9. Accelerated Stress Corrosion Crack Initiation of Alloys 600 and 690 in Hydrogenated Supercritical Water

    Science.gov (United States)

    Moss, Tyler; Was, Gary S.

    2017-01-01

    The objective of this study is to determine whether stress corrosion crack initiation of Alloys 600 and 690 occurs by the same mechanism in subcritical and supercritical water. Tensile bars of Alloys 690 and 600 were strained in constant extension rate tensile experiments in hydrogenated subcritical and supercritical water from 593 K to 723 K (320 °C to 450 °C), and the crack initiation behavior was characterized by high-resolution electron microscopy. Intergranular cracking was observed across the entire temperature range, and the morphology, structure, composition, and temperature dependence of initiated cracks in Alloy 690 were consistent between hydrogenated subcritical and supercritical water. Crack initiation of Alloy 600 followed an Arrhenius relationship and did not exhibit a discontinuity or change in slope after crossing the critical temperature. The measured activation energy was 121 ± 13 kJ/mol. Stress corrosion crack initiation in Alloy 690 was fit with a single activation energy of 92 ± 12 kJ/mol across the entire temperature range. Cracks were observed to propagate along grain boundaries adjacent to chromium-depleted metal, with Cr2O3 observed ahead of crack tips. All measures of the SCC behavior indicate that the mechanism for stress corrosion crack initiation of Alloy 600 and Alloy 690 is consistent between hydrogenated subcritical and supercritical water.

  10. Improved electron transport layer

    DEFF Research Database (Denmark)

    2012-01-01

    The present invention provides: a method of preparing a coating ink for forming a zinc oxide electron transport layer, comprising mixing zinc acetate and a wetting agent in water or methanol; a coating ink comprising zinc acetate and a wetting agent in aqueous solution or methanolic solution...

  11. Methanol production method and system

    Science.gov (United States)

    Chen, Michael J.; Rathke, Jerome W.

    1984-01-01

    Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

  12. Adsorption from Experimental Isotherms of Supercritical Gases

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A mathematical method was proposed for the determination of absolute adsorption from experimental isotherms. The method is based on the numerical equality of the absolute and the excess adsorption when either the gas phase density or the amount adsorbed is not quite considerable. The initial part of the experimental isotherms, which represents the absolute adsorption, became linear with some mathematical manipulations. The linear isotherms were reliably formulated. As consequence, either the volume or the density of the supercritical adsorbate could be determined by a non-empirical way. This method was illustrated by the adsorption data of supercritical hydrogen and methane on a superactivated carbon in large ranges of temperature and pressure.

  13. Charting the landscape of supercritical string theory

    CERN Document Server

    Hellerman, Simeon

    2007-01-01

    Special solutions of string theory in supercritical dimensions can interpolate in time between theories with different numbers of spacetime dimensions (via dimension quenching) and different amounts of worldsheet supersymmetry (via c-duality). These solutions connect supercritical string theories to the more familiar string duality web in ten dimensions, and provide a precise link between supersymmetric and purely bosonic string theories. Dimension quenching and c-duality appear to be natural concepts in string theory, giving rise to large networks of interconnected theories. We describe some of these networks in detail and discuss general consistency constraints on the types of transitions that arise in this framework.

  14. Withanolide artifacts formed in methanol.

    Science.gov (United States)

    Cao, Cong-Mei; Zhang, Huaping; Gallagher, Robert J; Timmermann, Barbara N

    2013-11-22

    Methanol solutions of the main withanolides (6-8) naturally present in Physalis longifolia yielded five artificial withanolides (1-5), including three new compounds (1-3). Withanolides 1 and 2 were identified as intramolecular Michael addition derivatives, while withanolides 3-5 were the result of intermolecular Michael addition. A comprehensive literature investigation was conducted to identify potential withanolide Michael addition artifacts isolated from Solanaceous species to date.

  15. Room temperature stable CO x -free H2 production from methanol with magnesium oxide nanophotocatalysts.

    Science.gov (United States)

    Liu, Zhengqing; Yin, Zongyou; Cox, Casandra; Bosman, Michel; Qian, Xiaofeng; Li, Na; Zhao, Hongyang; Du, Yaping; Li, Ju; Nocera, Daniel G

    2016-09-01

    Methanol, which contains 12.6 weight percent hydrogen, is a good hydrogen storage medium because it is a liquid at room temperature. However, by releasing the hydrogen, undesirable CO and/or CO2 byproducts are formed during catalytic fuel reforming. We show that alkaline earth metal oxides, in our case MgO nanocrystals, exhibit stable photocatalytic activity for CO/CO2-free H2 production from liquid methanol at room temperature. The performance of MgO nanocrystals toward methanol dehydrogenation increases with time and approaches ~320 μmol g(-1) hour(-1) after a 2-day photocatalytic reaction. The CO x -free H2 production is attributed to methanol photodecomposition to formaldehyde, photocatalyzed by surface electronic states of unique monodispersed, porous MgO nanocrystals, which were synthesized with a novel facile colloidal chemical strategy. An oxygen plasma treatment allows for the removal of organic surfactants, producing MgO nanocrystals that are well dispersible in methanol.

  16. The toxicity of inhaled methanol vapors

    Energy Technology Data Exchange (ETDEWEB)

    Kavet, R.; Nauss, K.M. (Environmental Research Information, Inc., Palo Alto, CA (USA))

    1990-01-01

    Methanol could become a major automotive fuel in the U.S., and its use may result in increased exposure of the public to methanol vapor. Nearly all of the available information on methanol toxicity in humans relates to the consequences of acute, rather than chronic, exposures. Acute methanol toxicity evolves in a well-understood pattern and consists of an uncompensated metabolic acidosis with superimposed toxicity to the visual system. The toxic properties of methanol are rooted in the factors that govern both the conversion of methanol to formic acid and the subsequent metabolism of formate to carbon dioxide in the folate pathway. In short, the toxic syndrome sets in if formate generation continues at a rate that exceeds its rate of metabolism. Current evidence indicates that formate accumulation will not challenge the metabolic capacity of the folate pathway at the anticipated levels of exposure to automotive methanol vapor.117 references.

  17. Low temperature synthesis of fibres composed of carbon-nickel nanoparticles in super-critical carbon dioxide

    Science.gov (United States)

    Hasumura, Takashi; Fukuda, Takahiro; Whitby, Raymond L. D.; Aschenbrenner, Ortrud; Maekawa, Toru

    2010-06-01

    We show that fibres composed of carbon-nickel nanoparticles are self-assembled by mixing nickelocene and oxygen with super-critical carbon dioxide in a dc electric field. The fibres grow in the direction of the electric field and the growth rate increases with an increase in the strength of the electric field. We also irradiate the fibres with electron beams and find that crystallized nickel particles are captured by carbon particles. The present result suggests that a low temperature method of creating carbon-metal hybrid nanostructures may be developed by mixing metallocene and trigger molecules with super-critical fluids subjected to a dc electric field.

  18. Hierarchical Biosilicates by the 3-D Replication of Block Copolymer Templates in Supercritical Fluids

    Science.gov (United States)

    2009-12-30

    replicated in metal oxides. The process involves the supercritical CO2-assisted infusion and phase selective condensation of silica precursors within one...cell biology of silica biomineralization . Protist 1998, 149, (3), 213-219. 19. Poulsen, N.; Sumper, M.; Kroger, N., Biosilica formation in diatoms...energy applications [electronic resource] : fabrication of mesoporous metal oxide films by 3-D replication of block copolymers. University of

  19. Supercritical synthesis and in situ deposition of PbS nanocrystals with oleic acid passivation for quantum dot solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Tavakoli, M.M. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Simchi, A., E-mail: simchi@sharif.edu [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Institute for Nanoscience and Nanotechnology, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of); Aashuri, H. [Department of Materials Science and Engineering, Sharif University of Technology, 14588 Tehran (Iran, Islamic Republic of)

    2015-04-15

    Colloidal quantum dot solar cells have recently attracted significant attention due to their low-processing cost and surging photovoltaic performance. In this paper, a novel, reproducible, and simple solution-based process based on supercritical fluid toluene is presented for in situ growth and deposition PbS nanocrystals with oleic-acid passivation. A lead precursor containing sulfur was mixed with oleic acid in toluene and processed in a supercritical fluid condition at different temperatures of 140, 270 and 330 °C for 20 min. The quantum dots were deposited on a fluorine-doped tin oxide glass substrate inside the supercritical reactor. Transmission electron microscopy, X-ray diffraction, absorption and dynamic light scattering showed that the nanocrystals processed at the supercritical condition (330 °C) are fully crystalline with a narrow size distribution of ∼3 nm with an absorption wavelength of 915 nm (bandgap of 1.3 eV). Fourier transform infrared spectroscopy indicated that the PbS quantum dots are passivated by oleic acid molecules during the growth. Photovoltaic characteristics of Schottky junction solar cells showed an improvement over devices prepared by spin-coating. - Highlights: • Supercritical fluid processing and in situ deposition of PbS QDs are presented. • The prepared nanocrystals are mono-dispersed with an optical bandgap of 1.3 eV. • Photovoltaic performance of the in situ deposited nanocrystals is reported. • An improved PV performance compared to spin coated Schottky solar cells is shown.

  20. Effect of Methanol on Photosynthesis and Chlorophyll Fluorescence of Flag Leaves of Winter Wheat

    Institute of Scientific and Technical Information of China (English)

    ZHENG Yue-jin; YANG Yue-qin; LIANG Shan-shan; YI Xian-feng

    2008-01-01

    Photosynthesis and chlorophyll a fluorescence parameters, photochemical efficiency of PS II (Fv/Fm), photochemical quenching of PS II (qP), nonphotochemical quenching of PS II (NPQ), maximum activity of PS II (Fv/Fo) as well as electron transport rate (ETR), and quantum yield of PS II (ΦPS II) were measured on flag leaves of the winter wheat treated by methanol at different concentrations. The results revealed that photosynthesis was greatly improved by methanol, as indicated by higher photosynthetic rates and stomatal conductance. The enhancement effect of methanol on photosynthesis was maintained for 3-4 days. Different methanol concentration treatments also increased intercellular CO2 concentration and transpiration rates. No significant decline was found in Fv/Fm, Fv/Fo, and ΦPS II, which revealed no photoinhibition during methanol application in different methanol concentrations. Methanol showing no apparent inhibitory effects indicated higher potential photosynthetic capacity of flag leaves of winter wheat. However, the increase in photosynthesis was not followed by an increase in the photosynthetic activity (Fv/Fm), and fluorescence parameters did not indicate an improvement in intercellular CO2 concentration and PS II photochemical efficiency compared with the control, thereby encouraging us to propose that lower leaf temperatures caused by applied methanol would reduce both dark respiration and photorespiration (most importantly), thus, increasing net CO2 uptake and photosynthetic rates.

  1. Supercritical carbondioxide extraction of cypermethrin in different ...

    African Journals Online (AJOL)

    STORAGESEVER

    2010-04-12

    Apr 12, 2010 ... century coincided with the development of industrial methods of cultivation ... though supercritical CO2 is a good solvent only for the extraction of non-polar to ..... 101-111. Lange's Handbook of Chemistry (1985) . ed. Dean JA ...

  2. Destruction of Energetic Materials in Supercritical Water

    Science.gov (United States)

    2002-06-25

    THERMOCHEMISTRY OF ENERGETIC MATERIALS IN SUPERCRITICAL WATER...fringe spacing is 13.5 µm and the acoustic signal period is 28.3 ns. 138 SECTION VI THERMOCHEMISTRY OF ENERGETIC MATERIALS IN...validation calculation studied the solvation free energies of alkali–chloride ion pairs in liquid water. Such information can teach us about the

  3. Supercritical fluid extraction and processing of foods

    Science.gov (United States)

    Consumers are aware of the processing techniques used to manufacture food and health supplements and are concerned about the impact of those processes on their health and the environment. Processes that use supercritical fluids as an alternative to solvents that are used to extract nutrients and bio...

  4. Supercritical-Multiple-Solvent Extraction From Coal

    Science.gov (United States)

    Corcoran, W.; Fong, W.; Pichaichanarong, P.; Chan, P.; Lawson, D.

    1983-01-01

    Large and small molecules dissolve different constituents. Experimental apparatus used to test supercritical extraction of hydrogen rich compounds from coal in various organic solvents. In decreasing order of importance, relevant process parameters were found to be temperature, solvent type, pressure, and residence time.

  5. Improved Supercritical-Solvent Extraction of Coal

    Science.gov (United States)

    Compton, L.

    1982-01-01

    Raw coal upgraded by supercritical-solvent extraction system that uses two materials instead of one. System achieved extraction yields of 20 to 49 weight percent. Single-solvent yields are about 25 weight percent. Experimental results show extraction yields may be timedependent. Observed decreases in weight of coal agreed well with increases in ash content of residue.

  6. Petrophysical core characterization at supercritical geothermal conditions

    Science.gov (United States)

    Kummerow, Juliane; Raab, Siegfried

    2015-04-01

    There is a growing scientific interest in the exploitation of supercritical geothermal reservoirs to increase the efficiency of geothermal power plants. The utilisation of geothermal energy requires in any case the detailed knowledge of the reservoir. In reservoir engineering, the characterisation of the geothermal system by electrical resistivity tomography (ERT) is a common geophysical exploration and monitoring strategy. For a realistic interpretation of the field measurements it is necessary to know both, the physical properties of the rock and those of the interacting fluid at defined temperature and pressure conditions. While there have been made great effort in determine the physical and chemical properties of water above its critical point (Tcritical = 374.21° C and pcritical = 221.2 bar), the influence of fluid-rock interactions on petrophysical properties in supercritical aqueous systems is nearly unknown. At supercritical conditions the viscosity of the fluid is low, which enhances the mass transfer and diffusion-controlled chemical reactions. This may have considerable effects on the porosity and hydraulic properties of a rock. To investigate high-enthalpy fluid-rock systems, in the framework of the EU-funded project IMAGE we have built a new percolation set-up, which allows for the measurement of electrical resistivity and permeability of rock samples at controlled supercritical conditions of aqueous fluids (pore pressure = 400 bar and a temperature = 400° C). First results will be presented.

  7. Comparison of Nitronic 50 and Stainless Steel 316 for use in Supercritical Water Environments

    Science.gov (United States)

    Karmiol, Zachary

    Increased efficiency can greatly benefit any mode of power production. Many proposed coal, natural gas, and nuclear reactors attempt to realize this goal through the use of increased operating temperatures and pressures, and as such require materials capable of withstanding extreme conditions. One such design employs supercritical water, which in addition to high temperatures and pressures is also highly oxidizing. A critical understanding of both mechanical and oxidation characteristics of candidate materials are required to determine the viability of materials for these reactors. This work investigates two potential materials, austenitic stainless steels, namely, Nitronic-50 and stainless steel 316, for use in these conditions. The supercritical water loop at the University of Nevada, Reno allowed for the study of materials at both subcritical and supercritical conditions. The materials were investigated mechanically using slow strain rate tests under conditions ranging from an inert nitrogen atmosphere, to both subcritical and supercritical water, with the failed samples surface characterized by optical microscopy, scanning electron microscopy, and Raman spectroscopy. Electrochemical studies were performed via potentiodynamic polarization in subcritical water only, and characterized using Raman spectroscopy. The samples were also exposed to supercritical water, and characterized using Raman spectroscopy. Nitronic-50 was found to have superior mechanical characteristics to stainless steel 316. SS-316 was found to have a surface film consisting of iron oxides, while the surface film of N-50 consisted predominantly of nickel-iron spinel. The crack interior of the sample was different from the exterior, indicating that the time and temperature of the exposure might play a defining role in determining the chemistry of the film.

  8. Metabolic methanol: molecular pathways and physiological roles.

    Science.gov (United States)

    Dorokhov, Yuri L; Shindyapina, Anastasia V; Sheshukova, Ekaterina V; Komarova, Tatiana V

    2015-04-01

    Methanol has been historically considered an exogenous product that leads only to pathological changes in the human body when consumed. However, in normal, healthy individuals, methanol and its short-lived oxidized product, formaldehyde, are naturally occurring compounds whose functions and origins have received limited attention. There are several sources of human physiological methanol. Fruits, vegetables, and alcoholic beverages are likely the main sources of exogenous methanol in the healthy human body. Metabolic methanol may occur as a result of fermentation by gut bacteria and metabolic processes involving S-adenosyl methionine. Regardless of its source, low levels of methanol in the body are maintained by physiological and metabolic clearance mechanisms. Although human blood contains small amounts of methanol and formaldehyde, the content of these molecules increases sharply after receiving even methanol-free ethanol, indicating an endogenous source of the metabolic methanol present at low levels in the blood regulated by a cluster of genes. Recent studies of the pathogenesis of neurological disorders indicate metabolic formaldehyde as a putative causative agent. The detection of increased formaldehyde content in the blood of both neurological patients and the elderly indicates the important role of genetic and biochemical mechanisms of maintaining low levels of methanol and formaldehyde.

  9. Endogenous methanol regulates mammalian gene activity.

    Directory of Open Access Journals (Sweden)

    Tatiana V Komarova

    Full Text Available We recently showed that methanol emitted by wounded plants might function as a signaling molecule for plant-to-plant and plant-to-animal communications. In mammals, methanol is considered a poison because the enzyme alcohol dehydrogenase (ADH converts methanol into toxic formaldehyde. However, the detection of methanol in the blood and exhaled air of healthy volunteers suggests that methanol may be a chemical with specific functions rather than a metabolic waste product. Using a genome-wide analysis of the mouse brain, we demonstrated that an increase in blood methanol concentration led to a change in the accumulation of mRNAs from genes primarily involved in detoxification processes and regulation of the alcohol/aldehyde dehydrogenases gene cluster. To test the role of ADH in the maintenance of low methanol concentration in the plasma, we used the specific ADH inhibitor 4-methylpyrazole (4-MP and showed that intraperitoneal administration of 4-MP resulted in a significant increase in the plasma methanol, ethanol and formaldehyde concentrations. Removal of the intestine significantly decreased the rate of methanol addition to the plasma and suggested that the gut flora may be involved in the endogenous production of methanol. ADH in the liver was identified as the main enzyme for metabolizing methanol because an increase in the methanol and ethanol contents in the liver homogenate was observed after 4-MP administration into the portal vein. Liver mRNA quantification showed changes in the accumulation of mRNAs from genes involved in cell signalling and detoxification processes. We hypothesized that endogenous methanol acts as a regulator of homeostasis by controlling the mRNA synthesis.

  10. Hydrogen Bonding Interaction between Atmospheric Gaseous Amides and Methanol.

    Science.gov (United States)

    Zhao, Hailiang; Tang, Shanshan; Xu, Xiang; Du, Lin

    2016-12-30

    Amides are important atmospheric organic-nitrogen compounds. Hydrogen bonded complexes of methanol (MeOH) with amides (formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide and N,N-dimethylacetamide) have been investigated. The carbonyl oxygen of the amides behaves as a hydrogen bond acceptor and the NH group of the amides acts as a hydrogen bond donor. The dominant hydrogen bonding interaction occurs between the carbonyl oxygen and the OH group of methanol as well as the interaction between the NH group of amides and the oxygen of methanol. However, the hydrogen bonds between the CH group and the carbonyl oxygen or the oxygen of methanol are also important for the overall stability of the complexes. Comparable red shifts of the C=O, NH- and OH-stretching transitions were found in these MeOH-amide complexes with considerable intensity enhancement. Topological analysis shows that the electron density at the bond critical points of the complexes fall in the range of hydrogen bonding criteria, and the Laplacian of charge density of the O-H∙∙∙O hydrogen bond slightly exceeds the upper value of the Laplacian criteria. The energy decomposition analysis further suggests that the hydrogen bonding interaction energies can be mainly attributed to the electrostatic, exchange and dispersion components.

  11. Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol.

    Science.gov (United States)

    Alberico, E; Nielsen, M

    2015-04-21

    The possibility to implement both the exhaustive dehydrogenation of aqueous methanol to hydrogen and CO2 and the reverse reaction, the hydrogenation of CO2 to methanol and water, may pave the way to a methanol based economy as part of a promising renewable energy system. Recently, homogeneous catalytic systems have been reported which are able to promote either one or the other of the two reactions under mild conditions. Here, we review and discuss these developments.

  12. Comprehensive Review of Applicable Supercritical Fluid Extraction Research

    Energy Technology Data Exchange (ETDEWEB)

    Harvey, Scott; Wright, Cherylyn W.; Wright, Bob W.

    2001-09-10

    This comprehensive supercritical fluid extraction (SFE) literature review is divided into three major sections. The first section describes the electronic literature search details including the abstract service used and the different topics searched. This section also contains an overview of the seven search topics that yielded relevant references along with a brief synopsis of the most significant literature citations. These seven groupings are (1) chemical warfare agents; (2) explosives; (3) hazardous chemicals; (4) poisons, toxins and mycotoxins; (5) toxic (lethal) chemical and toxicants; (6) pesticides in soil; and (7) pesticides from plant and animal tissues. The second section contains tables of each of these groupings. Each of the seven tables contains entries for individual literature citations listed along with the specific compounds or compound classes that are addressed. The third section refers to the abstracts used in the literature search.

  13. Corrosion behavior of Hastelloy C-276 in supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Qiang [National Key Laboratory for Nuclear Fuel and Materials, Nuclear Power Institute of China, P.O. Box 436, Chendu 610041 (China); Tang Rui [National Key Laboratory for Nuclear Fuel and Materials, Nuclear Power Institute of China, P.O. Box 436, Chendu 610041 (China)], E-mail: xajttr@163.com; Yin Kaiju; Luo Xin [National Key Laboratory for Nuclear Fuel and Materials, Nuclear Power Institute of China, P.O. Box 436, Chendu 610041 (China); Zhang Lefu [College of Nuclear Science and Technology, Shanghai Jiaotong University, Shanghai 200240 (China)

    2009-09-15

    The corrosion behavior of a nickel-based alloy Hastelloy C-276 exposed in supercritical water at 500-600 deg. C/25 MPa was investigated by means of gravimetry, scanning electron microscopy/energy dispersive X-ray spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. An oxide scale with dual-layer structure, mainly consisting of an outer NiO layer and an inner Cr{sub 2}O{sub 3}/NiCr{sub 2}O{sub 4}-mixed layer, developed on C-276 after 1000 h exposure. Higher temperature promoted oxidation, resulting in thicker oxide scale, larger weight gain and stronger tendency of oxide spallation. The oxide growth mechanism in SCW seems to be similar to that in high temperature water vapor, namely solid-state growth mechanism.

  14. Combustion characteristics of Methanol-base fuel(MBF)made by coal

    Institute of Scientific and Technical Information of China (English)

    ZHANG Quan; ZHAO Cong-cong; LIU Yang

    2011-01-01

    Profound experimental research was made on Methanol-base fuel(MBF)mainly consisting of methanol,and the results were compared with that of diesel oil.Their respective combustion characteristics of caloric value,combustion efficiency and components of smoke were synthetically analyzed by employing the electronic weighing devices,the rotor flow-meter,intelligent flue gas analyzer,advanced bomb calorimeter,etc.,referring to the feasibility of taking it as a fuel for general use.Experiment results show that Methanol-base fuel not only has superiorities on combustion characteristics but also bears energy saving and environmental protection advantages.

  15. New Rh-ZnO/Carbon Nanotubes Catalyst for Methanol Synthesis

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.

  16. Simultaneous analysis for water- and fat-soluble vitamins by a novel single chromatography technique unifying supercritical fluid chromatography and liquid chromatography.

    Science.gov (United States)

    Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

    2014-10-03

    Chromatography techniques usually use a single state in the mobile phase, such as liquid, gas, or supercritical fluid. Chromatographers manage one of these techniques for their purpose but are sometimes required to use multiple methods, or even worse, multiple techniques when the target compounds have a wide range of chemical properties. To overcome this challenge, we developed a single method covering a diverse compound range by means of a "unified" chromatography which completely bridges supercritical fluid chromatography and liquid chromatography. In our method, the phase state was continuously changed in the following order; supercritical, subcritical and liquid. Moreover, the gradient of the mobile phase starting at almost 100% CO2 was replaced with 100% methanol at the end completely. As a result, this approach achieved further extension of the polarity range of the mobile phase in a single run, and successfully enabled the simultaneous analysis of fat- and water-soluble vitamins with a wide logP range of -2.11 to 10.12. Furthermore, the 17 vitamins were exceptionally separated in 4min. Our results indicated that the use of dense CO2 and the replacement of CO2 by methanol are practical approaches in unified chromatography covering diverse compounds. Additionally, this is a first report to apply the novel approach to unified chromatography, and can open another door for diverse compound analysis in a single chromatographic technique with single injection, single column and single system.

  17. Optimization of supercritical fluid consecutive extractions of fatty acids and polyphenols from Vitis vinifera grape wastes.

    Science.gov (United States)

    Aizpurua-Olaizola, Oier; Ormazabal, Markel; Vallejo, Asier; Olivares, Maitane; Navarro, Patricia; Etxebarria, Nestor; Usobiaga, Aresatz

    2015-01-01

    In this study, supercritical fluid extraction has been successfully applied to a sequential fractionation of fatty acids and polyphenols from wine wastes (2 different vitis vinifera grapes). To this aim, in a 1st step just fatty acids were extracted and in a 2nd one the polyphenols. The variables that affected to the extraction efficiency were separately optimized in both steps following an experimental design approach. The effect of extraction temperature flow, pressure, and time were thoroughly evaluated for the extraction of fatty acids, whereas the addition of methanol was also considered in the case of the polyphenols extraction. A quantitative extraction with high efficiency was achieved at a very short time and low temperatures. Concerning quantification, fatty acids were determined by means of gas chromatography coupled to mass spectrometry after a derivatization step, whereas the polyphenols were analyzed by means of high performance liquid chromatography coupled to tandem mass spectrometry and the Folin-Ciocalteu method.

  18. Theoretical Studies on Critical Properties of Binary System with Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new expression of mixing rule is suggested according to the Mayson′s mixing rule in this paper, which adopts the Redlich-Kwong cubic equation of state and the modified Chueh-Prausnitz method to calculate the experiment critical points of six binary mixtures CO2+toluene, CO2+cyclohexane, CO2+n-butanal, CO2+i-butanal, CO2+methanol, CO2+ethanol. The coefficients of interaction parameter in the expression of mixing rule were optimized from experimental data. The calculated results of critical temperature and critical pressure meet the experiment data well. The maximum relative errors of temperature and pressure between the calculation results and experiment data are 1.493% and 5.2236% respectively, indicating that the proposed expression of mixing rule is reasonable. This may provide a fundamental method for studying and predicting the properties of supercritical fluids.

  19. Continuous catalyst-free methanolysis and ethanolysis of soybean oil under supercritical alcohol/water mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Vieitez, Ignacio; Grompone, Maria A.; Jachmanian, Ivan [Laboratorio de Grasas y Aceites, Departamento de Alimentos, Facultad de Quimica, Universidad de la Republica, Montevideo 11800 (Uruguay); da Silva, Camila; Alckmin, Isabella; Borges, Gustavo R.; Corazza, Fernanda C.; Oliveira, J. Vladimir [Department of Food Engineering, URI-Campus de Erechim, Erechim 99700-000 (Brazil)

    2010-09-15

    This work investigates and compares the reaction performance of soybean oil transesterification under supercritical methanol and ethanol, in a continuous catalyst-free process, as a cleaner alternative to conventional chemically catalyzed process. Reactions were performed in a tubular reactor, at 20 MPa, with oil to alcohol ratio of 1:40, varying the temperature in the range from 250 C to 350 C, and at two levels of water concentrations, 0 and 10 wt%. Although both processes proceeded with a relatively high reaction rate, conversion achieved by methanolysis was higher than that obtained by ethanolysis. Water positively affected both process: higher ester content and triacylglycerols depletion occurred when 10 wt% water was used compared with anhydrous conditions. Temperature increase favored the conversion of soybean oil to the corresponding methyl or ethyl esters, although temperatures above 300 C increased the fatty acid degradation degree, a phenomenon responsible for the low ester contents obtained at the highest temperatures and lowest flow rates studied. (author)

  20. Combined theoretical and experimental study on the adsorption of methanol on the ZnO(1010) surface.

    Science.gov (United States)

    Kiss, J; Langenberg, D; Silber, D; Traeger, F; Jin, L; Qiu, H; Wang, Y; Meyer, B; Wöll, Ch

    2011-06-30

    The structure, dynamics, and energetics of methanol adlayers on the nonpolar ZnO(1010) surface have been studied by He-atom diffraction (HAS), high-resolution electron energy loss spectroscopy (HREELS), thermal desorption spectroscopy (TDS), and density functional calculations. The experimental and theoretical data consistently show that at temperatures below 357 K methanol forms an ordered adlayer with a (2 × 1) periodicity and a coverage of one monolayer in which half of the methanol molecules are dissociated. The ordering of the methanol molecules is governed by repulsive interactions between the methyl groups of the methanol molecules. This repulsive interaction is also responsible for the formation of a second, low-density phase at higher temperatures with half monolayer coverage of undissociated methanol which is stable up to 440 K.

  1. Recovery of Minerals in Martian Soils Via Supercritical Fluid Extraction

    Science.gov (United States)

    Debelak, Kenneth A.; Roth, John A.

    2001-03-01

    We are investigating the use of supercritical fluids to extract mineral and/or carbonaceous material from Martian surface soils and its igneous crust. Two candidate supercritical fluids are carbon dioxide and water. The Martian atmosphere is composed mostly of carbon dioxide (approx. 95.3%) and could therefore provide an in-situ source of carbon dioxide. Water, although present in the Martian atmosphere at only approx. 0.03%, is also a candidate supercritical solvent. Previous work done with supercritical fluids has focused primarily on their solvating properties with organic compounds. Interestingly, the first work reported by Hannay and Hogarth at a meeting of the Royal Society of London in 1879 observed that increasing or decreasing the pressure caused several inorganic salts e.g., cobalt chloride, potassium iodide, and potassium bromide, to dissolve or precipitate in supercritical ethanol. In high-pressure boilers, silica, present in most boiler feed waters, is dissolved in supercritical steam and transported as dissolved silica to the turbine blades. As the pressure is reduced the silica precipitates onto the turbine blades eventually requiring the shutdown of the generator. In supercritical water oxidation processes for waste treatment, dissolved salts present a similar problem. The solubility of silicon dioxide (SiO2) in supercritical water is shown. The solubility curve has a shape characteristic of supercritical systems. At a high pressure (greater than 1750 atmospheres) increasing the temperature results in an increase in solubility of silica, while at low pressures, less than 400 atm., the solubility decreases as temperature increases. There are only a few studies in the literature where supercritical fluids are used in extractive metallurgy. Bolt modified the Mond process in which supercritical carbon monoxide was used to produce nickel carbonyl (Ni(CO)4). Tolley and Tester studied the solubility of titanium tetrachloride (TiCl4) in supercritical CO2

  2. Relating Direct Methanol Fuel Cell Performance to Measurements in a Liquid Half Cell

    DEFF Research Database (Denmark)

    Pedersen, Christoffer Mølleskov; Tynelius, Oskar; Lund-Olesen, Torsten

    2015-01-01

    Direct methanol fuel cells (DMFC) could act as a replacement for batteries in low power electronics. For instance, micro—DMFC’s could be used to power hearing instruments[1]. The power output of a DMFC is limited by the sluggish kinetics of both the methanol oxidation reaction (MOR) on the anode ...... Cells Bull. 2012 (2012) 12–16. doi:10.1016/S1464-2859(12)70367-X....

  3. [Harmful elements removal from Polygonum multiflorum by supercritical CO2 extraction].

    Science.gov (United States)

    Wen, Zhen; Liu, Bo; Zheng, Zong-Kun; You, Xin-Kui; Pu, Yi-Tao; Dang, Zhi

    2008-10-01

    To remove harmful elements as copper, lead and arsenic from Polygonum multiflorum, a Chinese traditional medicine, by supercritical carbon dioxide extraction. With sodium diethyldithiocarbamate (NaDDC) as a chelating agent and ethanol as a modifier, the effects of extraction style, time, pressure, temperature and amount of chelating agent on chelating extraction process were discussed. The condition was optimized as following: 28 MP as extraction pressure, 60 degrees C as extraction temperature, 1 h as static extraction time, 2 h as dynamic extraction time, m(herb) : m(NaDDC) = 5 : 1, m(herb) : m(ethanol) = 1 : 1. Under this condition, the extraction rate of Cu, Pb and As were up to 60% which achieved US FDA standard, while the physioloically active substance of 2,3,5,4'-tetrahydroxy-silbene-2-O-beta-D-glucoside was not extracted. The results show chelating extraction by supercritical CO2 can provide a non-destructive method to decrease the content of harmful elements from Chinese traditional medicines.

  4. [Supercritical CO2 fluid extraction and component analysis of leaves oil from Taxus chinensis var. mairei].

    Science.gov (United States)

    Tang, Bin; Zhang, Feng-su; Li, Xiang; Chen, Jian-wei; Yao, Xiao

    2013-12-01

    To research the optimal extraction process of supercritical CO2 extraction and analyze the component of the oil extracted from leaves of Taxus chinensis var. mairei. Using the yield of leaves oil from Taxus chinensis var. mairei as the index, investigated the effect of the extraction pressure, extraction temperature and extraction time on the extracting-rate of leaves oil. The chemical composition of the extracted leaves oil was analyzed by derivatized GC-MS. The optimal parameters of the supercritical CO2 extraction of the oil extracted from leaves of Taxus chinensis var. mairei were determined: CO2 compressor pump frequency was 10 Hz, the extraction pressure was 25 MPa and the temperature of extraction was 45 degrees C, the extraction time was 120 min, the isolator I pressure was 8.0 MPa and the temperature of extraction was 40 degrees C, the isolator II pressure was 5.0 MPa and the temperature of extraction was 35 degrees C. The extracted leaves oil was derivatized with boron trifluoride-methanol complex. Thirty-three kinds of fatty acids were identified by GC-MS. The yield of leaves oils are different from Taxus chinensis var. mairei from 3 habitats. The yield of leaves oil from Donggang, Wuxi city is the highest, about 2.61%. The kinds of fatty acids with high amounts in leaves oil from Taxus chinensis var. mairei is identical in general, the kinds of fatty acids with low amounts in leaves oil from Taxus chinensis var. mairei have differences.

  5. Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

    Science.gov (United States)

    Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

    2016-04-29

    An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method.

  6. Improvement of biodiesel methanol blends

    Directory of Open Access Journals (Sweden)

    Y. Datta Bharadwaz

    2016-06-01

    Full Text Available The main objective of this work was to improve the performance of biodiesel–methanol blends in a VCR engine by using optimized engine parameters. For optimization of the engine, operational parameters such as compression ratio, fuel blend, and load are taken as factors, whereas performance parameters such as brake thermal efficiency (Bth and brake specific fuel consumption (Bsfc and emission parameters such as carbon monoxide (CO, unburnt hydrocarbons (HC, Nitric oxides (NOx and smoke are taken as responses. Experimentation is carried out as per the design of experiments of the response surface methodology. Optimization of engine operational parameters is carried out using Derringers Desirability approach. From the results obtained it is inferred that the VCR engine has maximum performance and minimum emissions at 18 compression ratio, 5% fuel blend and at 9.03 kg of load. At this optimized operating conditions of the engine the responses such as brake thermal efficiency, brake specific fuel consumption, carbon monoxide, unburnt hydrocarbons, nitric oxide, and smoke are found to be 31.95%, 0.37 kg/kW h, 0.036%, 5 ppm, 531.23 ppm and 15.35% respectively. It is finally observed from the mathematical models and experimental data that biodiesel methanol blends have maximum efficiency and minimum emissions at optimized engine parameters.

  7. Bio-oil production from biomass via supercritical fluid extraction

    Energy Technology Data Exchange (ETDEWEB)

    Durak, Halil, E-mail: halildurak@yyu.edu.tr [Yuzuncu Yıl University, Vocational School of Health Services, 65080, Van (Turkey)

    2016-04-18

    Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

  8. Supercritical Fluids Processing of Biomass to Chemicals and Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Olson, Norman K. [Iowa State Univ., Ames, IA (United States)

    2011-09-28

    The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect to the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”

  9. Bio-oil production from biomass via supercritical fluid extraction

    Science.gov (United States)

    Durak, Halil

    2016-04-01

    Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

  10. Preparation of 5-fluorouracil nanoparticles by supercritical antisolvents for pulmonary delivery

    Directory of Open Access Journals (Sweden)

    Pardis Kalantarian

    2010-09-01

    Full Text Available Pardis Kalantarian1,2, Abdolhosein Rouholamini Najafabadi1, Ismaeil Haririan2, Alireza Vatanara1, Yadollah Yamini3, Majid Darabi1, Kambiz Gilani11Aerosol Research Laboratory and 2Pharmaceutical Laboratory, School of Pharmacy, Tehran University of Medical Sciences, 3Department of Chemistry, Tarbiat Modarres University, Tehran, IranAbstract: This study concerns the supercritical antisolvent process which allows single-step production of 5-fluorouracil (5-FU nanoparticles. This process enhances the physical characteristics of 5-FU in order to deliver it directly to the respiratory tract. Several mixtures of methanol with dichloromethane, acetone, or ethanol were used for particle preparation, and their effects on the physical characteristics of the final products were studied. The conditions of the experiment included pressures of 100 and 150 bar, temperature of 40°C, and a flow rate of 1 mL/min. The particles were characterized physicochemically before and after the process for their morphology and crystallinity. In spite of differences in size, the particles were not very different regarding their morphology. The resulting particles were of a regular shape, partly spherical, and appeared to have a smooth surface, whereas the mechanically milled particles showed less uniformity, had surface irregularities and a high particle size distribution, and seemed aggregated. Particles of 5-FU precipitated from methanol-dichloromethane 50:50 had a mean particle size of 248 nm. In order to evaluate the aerodynamic behavior of the nanoparticles, six 5-FU dry powder formulations containing mixtures of coarse and fine lactose of different percentages were prepared. Deposition of 5-FU was measured using a twin-stage liquid impinger and analyzed using a validated high pressure liquid chromatography method. Addition of fine lactose improved the aerodynamic performance of the drug, as determined by the fine particle fraction.Keywords: supercritical antisolvent, 5

  11. Industrial applications and current trends in supercritical fluid technologies

    OpenAIRE

    Gamse Thomas

    2005-01-01

    Supercritical fluids have a great potential for wide fields of processes Although CO2 is still one of the most used supercritical gases, for special purposes propane or even fluorinated-chlorinated fluids have also been tested. The specific characteristics of supercritical fluids behaviour were analyzed such as for example the solubilities of different components and the phase equilibria between the solute and solvent. The application at industrial scale (decaffeinating of tea and coffee, hop...

  12. Supercritical water oxidation of products of human metabolism

    Science.gov (United States)

    Tester, Jefferson W.; Orge A. achelling, Richard K. ADTHOMASSON; Orge A. achelling, Richard K. ADTHOMASSON

    1986-01-01

    Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

  13. Solubility and Phase Behavior of CL20 in Supercritical Fluids

    Science.gov (United States)

    2006-09-01

    supercritical state. The fugacity of the solute in the supercritical fluid can be evaluated using a cubic equation of state such as the Redlich - Kwong ...pro- gram was validated using available literature data for the solubility of naphthalene and of biphenyl in supercritical CO2. The applicability of...promising process using environmentally benign compressed gases as either solvents or anti-solvents is being investi- gated for applications in

  14. Ab initio molecular dynamics simulation study of successive hydrogenation reactions of carbon monoxide producing methanol

    Science.gov (United States)

    Pham, Thi Nu; Ono, Shota; Ohno, Kaoru

    2016-04-01

    Doing ab initio molecular dynamics simulations, we demonstrate a possibility of hydrogenation of carbon monoxide producing methanol step by step. At first, the hydrogen atom reacts with the carbon monoxide molecule at the excited state forming the formyl radical. Formaldehyde was formed after adding one more hydrogen atom to the system. Finally, absorption of two hydrogen atoms to formaldehyde produces methanol molecule. This study is performed by using the all-electron mixed basis approach based on the time dependent density functional theory within the adiabatic local density approximation for an electronic ground-state configuration and the one-shot GW approximation for an electronic excited state configuration.

  15. Supercritical CO{sub 2} mediated synthesis and catalytic activity of graphene/Pd nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Lulu [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Nguyen, Van Hoa [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of); Department of Chemistry, Nha Trang University, 2 Nguyen Dinh Chieu, Nha Trang (Viet Nam); Shim, Jae-Jin, E-mail: jjshim@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeoungbuk 712-749 (Korea, Republic of)

    2015-11-15

    Highlights: • RGO/Pd composite was efficiently prepared via a facile method in supercritical CO{sub 2}. • Graphene sheets were coated uniformly with Pd nanoparticles with a size of ∼8 nm. • Composites exhibited excellent catalytic activity in the Suzuki reaction even after 10 cycles. - Abstract: Graphene sheets were decorated with palladium nanoparticles using a facile and efficient method in supercritical CO{sub 2}. The nanoparticles were formed on the graphene sheets by the simple hydrogen reduction of palladium(II) hexafluoroacetylacetonate precursor in supercritical CO{sub 2}. The product was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Highly dispersed nanoparticles with various sizes and shapes adhered well to the graphene sheets. The composites showed high catalytic activities for the Suzuki reaction under aqueous and aerobic conditions within 5 min. The effects of the different Pd precursor loadings on the catalytic activities of the composites were also examined.

  16. Supercritical Water Process for the Chemical Recycling of Waste Plastics

    Science.gov (United States)

    Goto, Motonobu

    2010-11-01

    The development of chemical recycling of waste plastics by decomposition reactions in sub- and supercritical water is reviewed. Decomposition reactions proceed rapidly and selectively using supercritical fluids compared to conventional processes. Condensation polymerization plastics such as PET, nylon, and polyurethane, are relatively easily depolymerized to their monomers in supercritical water. The monomer components are recovered in high yield. Addition polymerization plastics such as phenol resin, epoxy resin, and polyethylene, are also decomposed to monomer components with or without catalysts. Recycling process of fiber reinforced plastics has been studied. Pilot scale or commercial scale plants have been developed and are operating with sub- and supercritical fluids.

  17. Supercritical Water Liquefaction of Coal and Waste Tires

    National Research Council Canada - National Science Library

    Prapan KUCHONTHARA; Yukihiko MATSUMURA

    2001-01-01

      Supercritical water liquefaction of scrap tire rubber and Ishikari coal, separately and in mixtures was investigated to study the possible synergetic effects of coliquefaction between the feedstocks...

  18. Dependence of Reaction Rate Constants on Density in Supercritical Fluids

    Institute of Scientific and Technical Information of China (English)

    WANGTao; SHENZhongyao

    2002-01-01

    A new method,which correlates rate constants of chemical reactions and density or pressure in supercritical fluids,was developed.Based on the transition state theory and thermodynamic principles, the rate constant can be reasonably correlated with the density of the supercritical fluid,and a correlation equation was obtained. Coupled with the equation of state (EOS) of a supercritical solvent,the effect of pressure on reaction rate constant could be represented.Two typical systems were used to test this method.The result indicates that this method is suitable for dilute supercritical fluid solutions.

  19. Reaction Behavior of Unsaturated Compounds in Sub- and Supercritical Water

    Institute of Scientific and Technical Information of China (English)

    K. Kobiro

    2005-01-01

    @@ 1Introduction Much attention has been paid on the chemistry of sub- and supercritical water, because of their unique prosperities such as low viscosity, low polarity, and high solubility to organic compounds[1]. Recently, the unique sub- and supercritical water is applied as reaction media and reaction catalysts for organic reactions[2,3].We herein disclose the unique reaction of unsaturated compounds in sub- and supercritical water with specific interaction between unsaturated bond(s) and high-density and high-energy water molecule(s) in sub- and supercritical water.

  20. Supercritical boiler material selection using fuzzy analytic network process

    Directory of Open Access Journals (Sweden)

    Saikat Ranjan Maity

    2012-08-01

    Full Text Available The recent development of world is being adversely affected by the scarcity of power and energy. To survive in the next generation, it is thus necessary to explore the non-conventional energy sources and efficiently consume the available sources. For efficient exploitation of the existing energy sources, a great scope lies in the use of Rankin cycle-based thermal power plants. Today, the gross efficiency of Rankin cycle-based thermal power plants is less than 28% which has been increased up to 40% with reheating and regenerative cycles. But, it can be further improved up to 47% by using supercritical power plant technology. Supercritical power plants use supercritical boilers which are able to withstand a very high temperature (650-720˚C and pressure (22.1 MPa while producing superheated steam. The thermal efficiency of a supercritical boiler greatly depends on the material of its different components. The supercritical boiler material should possess high creep rupture strength, high thermal conductivity, low thermal expansion, high specific heat and very high temperature withstandability. This paper considers a list of seven supercritical boiler materials whose performance is evaluated based on seven pivotal criteria. Given the intricacy and difficulty of this supercritical boiler material selection problem having interactions and interdependencies between different criteria, this paper applies fuzzy analytic network process to select the most appropriate material for a supercritical boiler. Rene 41 is the best supercritical boiler material, whereas, Haynes 230 is the worst preferred choice.

  1. H-1 Dynamic Nuclear Polarization in Supercritical Ethylene at 1.4 T

    Energy Technology Data Exchange (ETDEWEB)

    Wind, Robert A.(BATTELLE (PACIFIC NW LAB)); Shi, Bai (PNNL); Hu, Jian Zhi (BATTELLE (PACIFIC NW LAB)); Solum, Mark S.(Utah, Univ Of); Ellis, Paul D.(BATTELLE (PACIFIC NW LAB)); Grant, David M.(Utah, Univ Of); Pugmire, Ronald J.(Utah, Univ Of); Taylor, Craig M.(DOE); Yonker, Clement R.(BATTELLE (PACIFIC NW LAB))

    2000-03-01

    H1 dynamic nuclear polarization (DNP) has been measured in supercritical ethylene in the pressure range 60-300 bar and in an external field of 1.4 T. A single-cell sapphire tube was used as a high pressure cell and powdered 1,3-bisdiphenylene-2-phenyl allyl(BDPA) free radicals were added and distributed at the wall of the cell. At all pressures the dominant DNP effect was a positive Overhauser enhancement, caused by proton-electron contact interactions at the fluid/solid radical interface. The observed enhancements varied from 12 at 67 bar to 17 at 300 bar. Besides the Overhauser enhancement, also a small solid state and thermal mixing enhancement were observed, indicating that part of the ethylene is absorbed at the radical surface for a prolonged time. These data indicate that DNP-enhanced NMR has the potential of extending the impact of NMR in research areas involving supercritical fluids.

  2. The ETHANOL-CO_2 Dimer is AN Electron Donor-Acceptor Complex

    Science.gov (United States)

    McGuire, Brett A.; Martin-Drumel, Marie-Aline; McCarthy, Michael C.

    2017-06-01

    Supercritical (sc) CO_2 is a common industrial solvent for the extraction of caffeine, nicotine, petrochemicals, and natural products. The ability of apolar scCO_2 to dissolve polar solutes is greatly enhanced by the addition of a polar co-solvent, often methanol or ethanol. Experimental and theoretical work show that methanol interactions in scCO_2 are predominantly hydrogen bonding, while the gas-phase complex is an electron donor-acceptor (EDA) configuration. Ethanol, meanwhile, is predicted to form EDA complexes both in scCO_2 and in the gas phase, but there have been no experimental measurements to support this conclusion. Here, we report a combined chirped-pulse and cavity FTMW study of the ethanol-CO_2 complex. Comparison with theory indicates the EDA complex is dominant under our experimental conditions. We confirm the structure with isotopic substitution, and derive a semi-experimental equilibrium structure. Our results are consistent with theoretical predictions that the linearity of the CO_2 subgroup is broken by the complexation interaction.

  3. The pseudocritical regions for supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Imre, A.R., E-mail: imre.attila@energia.mta.hu [HAS Centre for Energy Research, Thermohydraulics Department, P.O. Box 49, H-1525 Budapest (Hungary); University Cologne, Institute for Physical Chemistry, Luxemburger Str. 116, D-50939 Koeln (Germany); Deiters, U.K.; Kraska, T. [University Cologne, Institute for Physical Chemistry, Luxemburger Str. 116, D-50939 Koeln (Germany); Tiselj, I. [Jozef Stefan Institute, Reactor Engineering Division, Jamova 39, 1000 Ljubljana (Slovenia)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Supercritical water behaves anomalously around the Widom lines. Black-Right-Pointing-Pointer We calculated the location of the Widom lines for several thermodynamic functions. Black-Right-Pointing-Pointer Simple quadratic fitting equations are given to describe these lines. - Abstract: Vapour pressure curves and stability lines can be extended beyond the critical points into the supercritical domain by so-called Widom lines, along which some thermodynamic property undergoes a rapid change and liquid-like behaviour turns to vapour-like one. Knowledge about such lines is therefore important for thermohydraulic calculations and design. There are several properties that can be chosen as defining property of a Widom line. In this short note we calculate and compare several kinds of Widom lines for water.

  4. Supercritical separation process for complex organic mixtures

    Science.gov (United States)

    Chum, Helena L.; Filardo, Giuseppe

    1990-01-01

    A process is disclosed for separating low molecular weight components from complex aqueous organic mixtures. The process includes preparing a separation solution of supercritical carbon dioxide with an effective amount of an entrainer to modify the solvation power of the supercritical carbon dioxide and extract preselected low molecular weight components. The separation solution is maintained at a temperature of at least about 70.degree. C. and a pressure of at least about 1,500 psi. The separation solution is then contacted with the organic mixtures while maintaining the temperature and pressure as above until the mixtures and solution reach equilibrium to extract the preselected low molecular weight components from the organic mixtures. Finally, the entrainer/extracted components portion of the equilibrium mixture is isolated from the separation solution.

  5. Supercritical Fluid Extraction of Flavonoids from Dandelion

    Directory of Open Access Journals (Sweden)

    Wu Jun

    2014-01-01

    Full Text Available In this study, the total flavonoids from dandelion was extracted by supercritical CO2 and the total flavonoids content in the extract was investigated by the sodium nitrite-aluminum nitrate method with Rutin as a standard product. Single-factor experiments were carried out to map the effects of extraction pressure, temperature, time and entrainer amount on the yield of flavonoids. The orthogonal experiments on the optimum technology parameters demonstrated that the influence of the experimental conditions over the yield from high to low was: (a pressure, (b temperature, (c entrainer amount, (d time. The optimization result showed that under the conditions of 50°C, 35 MPa, 80 min and 4.0 mL/g entrainer amount, the yield of the preparative supercritical fluid extraction was 4.974%.

  6. Stochastic simulation of supercritical fluid extraction processes

    Directory of Open Access Journals (Sweden)

    Mizutani F. T.

    2000-01-01

    Full Text Available Process simulation involves the evaluation of output variables by the specification of input variables and process parameters. However, in a real process, input data and parameters cannot be known without uncertainty. This fact may limit the utilization of simulation results to predict plant behavior. In order to achieve a more realistic analysis, the procedure of stochastic simulation can be conducted. This technique is based on a large set of simulation runs where input variables and parameters are randomly selected according to adequate probability density functions. The objective of this work is to illustrate the application of a stochastic simulation procedure to the process of fractionation of orange essential oil, using supercritical carbon dioxide in a multistage extraction column. Analysis of the proposed example demonstrates the importance of the stochastic simulation to develop more reliable designs and operating conditions for a supercritical fluid extraction process.

  7. Using supercritical fluids to refine hydrocarbons

    Science.gov (United States)

    Yarbro, Stephen Lee

    2014-11-25

    This is a method to reactively refine hydrocarbons, such as heavy oils with API gravities of less than 20.degree. and bitumen-like hydrocarbons with viscosities greater than 1000 cp at standard temperature and pressure using a selected fluid at supercritical conditions. The reaction portion of the method delivers lighter weight, more volatile hydrocarbons to an attached contacting device that operates in mixed subcritical or supercritical modes. This separates the reaction products into portions that are viable for use or sale without further conventional refining and hydro-processing techniques. This method produces valuable products with fewer processing steps, lower costs, increased worker safety due to less processing and handling, allow greater opportunity for new oil field development and subsequent positive economic impact, reduce related carbon dioxide, and wastes typical with conventional refineries.

  8. Methanol conversion to lower olefins over RHO type zeolite

    KAUST Repository

    Masih, Dilshad

    2013-07-01

    Eight-membered ring small-pore zeolite of RHO-type topology has been synthesized, characterized and tested for methanol-to-olefin (MTO) reaction. The zeolite was hydrothermally crystallized from the gel with Si/Al ratio of 5.0. It showed a high BET specific surface area (812 m2 g-1), micropore volume (0.429 cm3 g-1), and acid amount (2.53 mmol g-1). Scanning electron microscopy observations showed small crystallites of about 1 μm. The zeolite was active for MTO reaction with 100% methanol conversions at 623-723 K, whereas selectivity to lower olefins changed with time. © 2013 Elsevier B.V.

  9. Nafion/PTFE composite membranes for direct methanol fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Hsiu-Li; Yu, T. Leon; Chen, Li-Chung [Department of Chemical Engineering and Materials Science, Yuan Ze University, Nei-Li, Taoyuan 32026 (Taiwan); Huang, Li-Ning; Shen, Kun-Sheng; Jung, Guo-Bin [Fuel Cell Center, Yuan Ze University, Nei-Li, Taoyuan 32026 (Taiwan)

    2005-10-04

    Using dynamic light scattering and scanning electron microscope (SEM), it is shown that a high-carbon-number alcohol/water, i.e., 2-propanol/water, mixed solvent is more effective than low-carbon-number alcohol/water, i.e., ethanol/water and methanol/water, mixed solvents in dispersing Nafion molecules. Thus, it is a better solvent for the preparation of Nafion/PTFE (poly(tetrafluoroethylene)) composite membranes. The performance of direct methanol fuel cells (DMFCs) with a Nafion/PTFE composite membrane, which was prepared in-house, a commercial Nafion-117 membrane, or a commercial Nafion-112 membrane were investigated by feeding various concentrations, i.e., 2-5M, of methanol to the anode. The Nafion/PTFE composite membrane gave a better DMFC performance than that obtained with Nafion-117 or Nafion-112 membranes. Using a DMFC model and varying the methanol concentration at the anode, cell voltage data were analyzed with respect to methanol concentration and cell current. The results indicate that inserting porous PTFE into Nafion polymer causes a reduction not only in methanol diffusion cross-over but also in the electro-osmosis of methanol cross-over in the membrane. (author)

  10. Design and implementation of a wireless passive microsensor for methanol detection

    Science.gov (United States)

    Sanz, Diego; Rosas, Walter; Unigarro, Edgar; Vargas, Watson; Segura-Quijano, Fredy

    2013-03-01

    Methanol is a public health concern due to its toxicity, characterized by metabolic acidosis and blindness, among others. The third world population affected by the exposure to this compound is increasing, mainly due to the consumption of illicit distilled or adulterated alcoholic beverages. Although methanol is naturally present in some alcoholic drinks, the maximum allowed concentration cannot exceed 10 g of methanol per liter of anhydrous alcohol (0.4% (v/v) at 40% of ethanol) according to the general EU limit. A wireless passive microsensor was designed to detect small amounts of methanol at 40% of alcoholic dissolutions. The sensor consists of a planar inductor in series with an interdigital capacitor that changes its capacitance with the solution's dielectric constant. An antenna is used to readout the real part of the impedance to obtain the resonant frequencies for different amounts of methanol in the solution. The aim of this work was to develop a low cost wireless sensor with the capability to detect concentrations of at least 0.4% (v/v) of methanol in a 40% of alcoholic solution. The results obtained show variations of 403 kHz in the resonant frequency for changes of 0.2% (v/v) on the concentration of methanol in a 40% alcoholic ethanol-based solution. This project was possible thanks to the collaboration of the Department of Electrical and Electronics Engineering and the Department of Chemical Engineering of Universidad de los Andes.

  11. Dye solubility in supercritical carbon dioxide fluid

    Directory of Open Access Journals (Sweden)

    Yan Jun

    2015-01-01

    Full Text Available Supercritical carbon dioxide fluid is an alternative solvent for the water of the traditional dyeing. The solubility of dyestuff affects greatly the dyeing process. A theoretical model for predicting the dye solubility is proposed and verified experimentally. The paper concludes that the pressure has a greater impact on the dyestuff solubility than temperature, and an optimal dyeing condition is suggested for the highest distribution coefficient of dyestuff.

  12. Computational Modeling of Supercritical and Transcritical Flows

    Science.gov (United States)

    2017-01-09

    reasonably accurate for supercritical and transcritical combustion. 15. SUBJECT TERMS N/A 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF...pr Reduced pressure (p/pc) Tc Critical temperature Tr Reduced temperature (T/Tc) Vm Molar volume Xi Mole fraction of species i Z Compressibility ω...pressure states. A 5.5mm by 0.4064mm domain uses a uniform 256 × 512 Cartesian grid. The code is fifth order accurate in space and a third order

  13. Supercritical CO2 Extraction of Ethanol

    OpenAIRE

    GÜVENÇ, A.; MEHMETOĞLU, Ü.; ÇALIMLI, A.

    1999-01-01

    Extraction of ethanol was studied from both synthetic ethanol solution and fermentation broth using supercritical CO2 in an extraction apparatus in ranges of 313 to 333 K and 80 to 160 atmospheres, for varying extraction times. The experimental system consists mainly of four parts: a CO2 storage system, a high-pressure liquid pump, an extractor and a product collection unit. Samples were analyzed by gas chromatography. Effects of temperature, pressure, extraction time, initial ethan...

  14. Developmental and Reproductive Toxicology of Methanol

    Science.gov (United States)

    Methanol is a high production volume chemical used as a feedstock for chemical syntheses and as a solvent and fuel additive. Methanol is acutely toxic to humans, causing acidosis, blindness in death at high dosages, but its developmental and reproductive toxicity in humans is poo...

  15. Hydrogenation of carbon dioxide for methanol production

    NARCIS (Netherlands)

    Ham, van der A.G.J.; Berg, van den H.; Benneker, A.; Simmelink, G.; Timmer, J.; Weerden, van S.

    2012-01-01

    A process for the hydrogenation of CO2 to methanol with a capacity of 10 kt/y methanol is designed in a systematic way. The challenge will be to obtain a process with a high net CO2 conversion. From initially four conceptual designs the most feasible is selected and designed in more detail. The feed

  16. Quantification of 3-n-butylphthalide in beagle plasma samples by supercritical fluid chromatography with triple quadruple mass spectrometry and its application to an oral bioavailability study.

    Science.gov (United States)

    Li, Yun; Zhao, Longshan; Li, Xiaoting; Guo, Bei; Zhao, Juanhang; Wang, Xianglin; Zhang, Tianhong

    2015-02-01

    A high-throughput, rapid, sensitive, environmentally friendly, and economical supercritical fluid chromatography with triple quadruple mass spectrometry method was established and validated for the first time to determine a cerebral stroke treatment drug named 3-n-butylphthalide in dog plasma. Plasma samples were prepared by protein precipitation with methanol and the analytes were eluted on an ACQUITY UPC(2TM) HSS-C(18) SB column (3 × 100 mm, 1.8 μm) maintained at 50°C. The mobile phase comprised supercritical carbon dioxide/methanol (90:10, v/v) at a flow rate of 1.5 mL/min, the compensation solvent was methanol at a flow rate of 0.2 mL/min and the total run time was 1.5 min per sample. The detection was carried out on a tandem mass spectrometer with an electrospray ionization source. Calibration curves were linear over the concentration range of 1.02-1021.00 ng/mL (r(2) ≥ 0.993) with the lower limit of quantification of 1.02 ng/mL. The intra- and inter-day precision values were below 15% and the accuracy was from 97.90 to 103.70% at all quality control levels. The method was suitable for a pharmacokinetic study of 3-n-butylphthalide in beagle dogs.

  17. Advanced Thermal Storage for Central Receivers with Supercritical Coolants

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, Bruce D.

    2010-06-15

    The principal objective of the study is to determine if supercritical heat transport fluids in a central receiver power plant, in combination with ceramic thermocline storage systems, offer a reduction in levelized energy cost over a baseline nitrate salt concept. The baseline concept uses a nitrate salt receiver, two-tank (hot and cold) nitrate salt thermal storage, and a subcritical Rankine cycle. A total of 6 plant designs were analyzed, as follows: Plant Designation Receiver Fluid Thermal Storage Rankine Cycle Subcritical nitrate salt Nitrate salt Two tank nitrate salt Subcritical Supercritical nitrate salt Nitrate salt Two tank nitrate salt Supercritical Low temperature H2O Supercritical H2O Two tank nitrate salt Supercritical High temperature H2O Supercritical H2O Packed bed thermocline Supercritical Low temperature CO2 Supercritical CO2 Two tank nitrate salt Supercritical High temperature CO2 Supercritical CO2 Packed bed thermocline Supercritical Several conclusions have been drawn from the results of the study, as follows: 1) The use of supercritical H2O as the heat transport fluid in a packed bed thermocline is likely not a practical approach. The specific heat of the fluid is a strong function of the temperatures at values near 400 °C, and the temperature profile in the bed during a charging cycle is markedly different than the profile during a discharging cycle. 2) The use of supercritical CO2 as the heat transport fluid in a packed bed thermocline is judged to be technically feasible. Nonetheless, the high operating pressures for the supercritical fluid require the use of pressure vessels to contain the storage inventory. The unit cost of the two-tank nitrate salt system is approximately $24/kWht, while the unit cost of the high pressure thermocline system is nominally 10 times as high. 3) For the supercritical fluids, the outer crown temperatures of the receiver tubes are in the range of 700 to 800 °C. At temperatures of 700 °C and above

  18. Use of supercritical carbon dioxide extraction

    Energy Technology Data Exchange (ETDEWEB)

    Taniguchi, Masayuki (Niigata Univ., Faculty of Engineering, Niigata, (Japan))

    1989-09-25

    Supercritical fluid extraction is a novel diffusion and separation technique which exploits simultaneously the increase of vapor pressure and the difference of chemical affinities of fluids near the critical point. A solvent which is used as the supercritical fluid has the following features: the critical point exists in the position of relatively ease of handling, the solvent is applicable to the extraction of a physiological active substance of thermal instability. Carbon dioxide as the solvent is non-flammable, non-corrosive, non-toxic, cheap, and readily available of high purity. The results of studies on the use of supercritical carbon dioxide (SC-CO{sub 2}) as a solvent for natural products in the fermentation and food industries, were collected. SC-CO{sub 2} extraction are used in many fields, examples for the application are as follows: removal of organic solvents from antibiotics; extraction of vegetable oils contained in wheat germ oil, high quality mustard seeds, rice bran and so on; brewing of sake using rice and rice-koji; use as a non-aqueous medium for the synthesis of precursors of the Aspartame; and use in sterilization. 66 refs., 17 figs., 21 tabs.

  19. Recycling of greenhouse gases via methanol

    Energy Technology Data Exchange (ETDEWEB)

    Bill, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Eliasson, B.; Kogelschatz, U. [ABB Corporate Research Center, Baden-Daettwil (Switzerland)

    1997-06-01

    Greenhouse gas emissions to the atmosphere can be mitigated by using direct control technologies (capture, disposal or chemical recycling). We report on carbon dioxide and methane recycling with other chemicals, especially with hydrogen and oxygen, to methanol. Methanol synthesis from CO{sub 2} is investigated on various catalysts at moderate pressures ({<=}30 bar) and temperatures ({<=}300{sup o}C). The catalysts show good methanol activities and selectivities. The conversion of CO{sub 2} and CH{sub 4} to methanol is also studied in a silent electrical discharge at pressures of 1 to 4 bar and temperatures close to room temperature. Methanol yields are given for mixtures of CO{sub 2}/H{sub 2}, CH{sub 4}/O{sub 2} and also for CH{sub 4} and air mixtures. (author) 2 figs., 5 refs.

  20. A search for extragalactic methanol masers

    CERN Document Server

    Ellingsen, S P; Whiteoak, J B; Vaile, R A; McCulloch, P M; Price, M

    1994-01-01

    A sensitive search for 6.7--GHz methanol maser emission has been made towards 10 galaxies that have yielded detectable microwave molecular--line transitions. These include several which show OH megamaser or superluminous \\water\\/ maser emission. Within the Galaxy, \\methanol\\/ and OH masers often occur in the same star formation regions and, in most cases, the \\methanol\\/ masers have a greater peak flux density than their OH counterparts. Thus we might expect \\methanol\\/ masers to be associated with extragalactic OH maser sources. We failed to detect any emission or absorption above our 60--mJy detection limit. We conclude that if the physical conditions exist to produce \\methanol\\/ megamaser emission, they are incompatible with the conditions which produce OH megamaser emission.

  1. Production of methanol/DME from biomass

    DEFF Research Database (Denmark)

    Ahrenfeldt, Jesper; Henriksen, Ulrik Birk; Münster-Swendsen, Janus

    In this project the production of DME/methanol from biomass has been investigated. Production of DME/methanol from biomass requires the use of a gasifier to transform the solid fuel to a synthesis gas (syngas) - this syngas can then be catalytically converted to DME/methanol. Two different gasifier...... cleaning. This was proved by experiments. Thermodynamic computer models of DME and methanol plants based on using the Two-Stage Gasification concept were created to show the potential of such plants. The models showed that the potential biomass to DME/methanol + net electricity energy efficiency was 51...... gasification, but little information exists on using these types of gasifiers for biomass gasification. The experiments performed provided quantitative data on product and gas composition as a function of operation conditions. Biomass can be gasified with less oxygen consumption compared to coal. The organic...

  2. New catalysts for miniaturized methanol fuel cells

    DEFF Research Database (Denmark)

    Pedersen, Christoffer Mølleskov

    The methanol fuel cell is an interesting energy technology, capable of converting the chemical energy of methanol directly into electricity. The technology is specifically attractive for small mobile applications such as laptops, smartphones, tablets etc. since it offers almost instantaneously...... recharging by simply replacing the methanol liquid. The technology is currently being developed for hearing instruments in order to ease the handling of the device for users complaining about difficulties replacing the very small batteries in the hearing instrument. The technology has already been...... and methanol poisoning of the oxygen reduction are studied. Consequently, promising new candidates for replacing the standard catalyst are identified. One of these, Pt5Gd, exhibits improved oxygen reduction reaction activity even in the presence of methanol, thus making Pt5Gd an interesting candidate...

  3. Determination of binary diffusion coefficients in supercritical carbon dioxide with supercritical fluid chromatography (SFC)

    Energy Technology Data Exchange (ETDEWEB)

    Dahmen, N.; Duelberg, A.; Schneider, G.M. (Bochum Univ. (Germany, F.R.). Lehrstuhl fuer Physikalische Chemie 2)

    1990-03-01

    Binary diffusion coefficient D{sub 12} in supercritical carbon dioxide were determined in a Supercritical Fluid Chromatography (SFC) apparatus by the peak broadening method (PBM). Some cyclic and linear ketones were investigated as a function of pressure between 9.5 and 18 MPa at about 314 K corresponding to densities form 513 to 820 kg m{sup -3}. The resulting D{sub 12} values are of the order of 10{sup -8} m{sup 2} s{sup -1} and lnD{sub 12} decreases about linearly with increasing density {rho} of the CO{sub 2}. (orig.).

  4. Fabrication of a form- and size-variable microcellular-polymer-stabilized metal nanocomposite using supercritical foaming and impregnation for catalytic hydrogenation

    Science.gov (United States)

    Liao, Weisheng; Wu, Ben-Zen; Nian, Hungchi; Chen, Hsiang-Yu; Yu, Jya-Jyun; Chiu, KongHwa

    2012-05-01

    This article presents the fabrication of size-controllable and shape-flexible microcellular high-density polyethylene-stabilized palladium nanoparticles (Pd/m-HDPE) using supercritical foaming, followed by supercritical impregnation. These nanomaterials are investigated for use as heterogeneous hydrogenation catalysts of biphenyls in supercritical carbon dioxide with no significant surface and inner mass transfer resistance. The morphology of the Pd/m-HDPE is examined using scanning electron microscopy images of the pores inside Pd/m-HDPE catalysts and transmission electron microscopy images of the Pd particles confined in an HDPE structure. This nanocomposite simplifies industrial design and operation. These Pd/m-HDPE catalysts can be recycled easily and reused without complex recovery and cleaning procedures.

  5. Fabrication of Novel Titanium-supported Ni-Sn Catalysts for Methanol Electro-oxidation

    Institute of Scientific and Technical Information of China (English)

    YI Qing-Feng; HUANG Wu; YU Wen-Qiang; LI Lei; LIU Xiao-Ping

    2008-01-01

    Novel titanium-supported Ni-Sn/Ti electrodes (Ni8Sn/Ti, Ni7Sn3/Ti and Ni/Ti) have been prepared using a hydrothermal method by a one step process. The scanning electron microscopy (SEM) images show that the catalyst particles are present as nano-scale flakes. Their electrochemical activity for methanol oxidation in 1 mol·L-1 NaOH was evaluated using voltammetric techniques, chronoamperometric measurements and electrochemical impedance spectra (EIS). It was found that the Ni8Sn/Ti electrode presents higher anodic currents and lower onset potential for methanol oxidation than Ni7Sn3/Ti, Ni/Ti and polycrystalline Ni electrodes. The EIS data indicate that under condi- tions of various anodic potentials and methanol concentrations, the Ni8Sn/Ti electrode displays significantly lower charge transfer resistances and high electrocatalytic activity towards methanol oxidation.

  6. Characterization and evolution of an activator-independent methanol dehydrogenase from Cupriavidus necator N-1.

    Science.gov (United States)

    Wu, Tung-Yun; Chen, Chang-Ting; Liu, Jessica Tse-Jin; Bogorad, Igor W; Damoiseaux, Robert; Liao, James C

    2016-06-01

    Methanol utilization by methylotrophic or non-methylotrophic organisms is the first step toward methanol bioconversion to higher carbon-chain chemicals. Methanol oxidation using NAD-dependent methanol dehydrogenase (Mdh) is of particular interest because it uses NAD(+) as the electron carrier. To our knowledge, only a limited number of NAD-dependent Mdhs have been reported. The most studied is the Bacillus methanolicus Mdh, which exhibits low enzyme specificity to methanol and is dependent on an endogenous activator protein (ACT). In this work, we characterized and engineered a group III NAD-dependent alcohol dehydrogenase (Mdh2) from Cupriavidus necator N-1 (previously designated as Ralstonia eutropha). This enzyme is the first NAD-dependent Mdh characterized from a Gram-negative, mesophilic, non-methylotrophic organism with a significant activity towards methanol. Interestingly, unlike previously reported Mdhs, Mdh2 does not require activation by known activators such as B. methanolicus ACT and Escherichia coli Nudix hydrolase NudF, or putative native C. necator activators in the Nudix family under mesophilic conditions. This enzyme exhibited higher or comparable activity and affinity toward methanol relative to the B. methanolicus Mdh with or without ACT in a wide range of temperatures. Furthermore, using directed molecular evolution, we engineered a variant (CT4-1) of Mdh2 that showed a 6-fold higher K cat/K m for methanol and 10-fold lower K cat/K m for n-butanol. Thus, CT4-1 represents an NAD-dependent Mdh with much improved catalytic efficiency and specificity toward methanol compared with the existing NAD-dependent Mdhs with or without ACT activation.

  7. Supercritical Fluid Extraction of Quinones from Compost for Microbial Community Analysis

    Directory of Open Access Journals (Sweden)

    Ni Luh Gede Ratna Juliasih

    2015-01-01

    Full Text Available Supercritical fluid extraction (SFE was used to extract quinones from compost to monitor the microbial community dynamics during composting. The 0.3 g of dried compost was extracted using 3 mL min−1 of carbon dioxide (90% and methanol (10% at 45°C and 25 MPa for a 30 min extraction time. The extracted quinones were analysed using ultra performance liquid chromatography (UPLC with 0.3 mL min−1 of methanol mobile phase for a 50 min chromatographic run time. A comparable detected amount of quinones was obtained using the developed method and an organic solvent extraction method, being 36.06 μmol kg−1 and 34.54 μmol kg−1, respectively. Significantly low value of dissimilarity index (D between the two methods (0.05 indicated that the quinone profile obtained by both methods was considered identical. The developed method was then applied to determine the maturity of the compost by monitoring the change of quinone during composting. The UQ-9 and MK-7 were predominant quinones in the initial stage of composting. The diversity of quinone became more complex during the cooling and maturation stages. This study showed that SFE had successfully extracted quinones from a complex matrix with simplification and rapidity of the analysis that is beneficial for routine analysis.

  8. Continuous production of biodiesel from microalgae by extraction coupling with transesterification under supercritical conditions.

    Science.gov (United States)

    Zhou, Dan; Qiao, Baoquan; Li, Gen; Xue, Song; Yin, Jianzhong

    2017-08-01

    Raw material for biodiesel has been expanded from edible oil to non-edible oil. In this study, biodiesel continuous production for two kinds of microalgae Chrysophyta and Chlorella sp. was conducted. Coupling with the supercritical carbon dioxide extraction, the oil of microalgae was extracted firstly, and then sent to the downstream production of biodiesel. The residue after decompression can be reused as the material for pharmaceuticals and nutraceuticals. Results showed that the particle size of microalgae, temperature, pressure, molar ration of methanol to oil, flow of CO2 and n-hexane all have effects on the yield of biodiesel. With the optimal operation conditions: 40mesh algae, extraction temperature 60°C, flow of n-hexane 0.4ml/min, reaction temperature: 340°C, pressure: 18-20MPa, CO2 flow of 0.5L/min, molar ration of methanol to oil 84:1, a yield of 56.31% was obtained for Chrysophyta, and 63.78% for Chlorella sp. due to the higher lipid content. Copyright © 2017. Published by Elsevier Ltd.

  9. Supercritical Carbon Dioxide Extraction of Bioactive Compounds from Ampelopsis grossedentata Stems: Process Optimization and Antioxidant Activity

    Directory of Open Access Journals (Sweden)

    Da Sun

    2011-10-01

    Full Text Available Supercritical carbon dioxide (SC-CO2 extraction of bioactive compounds including flavonoids and phenolics from Ampelopsis grossedentata stems was carried out. Extraction parameters such as pressure, temperature, dynamic time and modifier, were optimized using an orthogonal array design of L9 (34, and antioxidant activities of the extracts were evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH free radical scavenging assay and ferrous ion chelating (FIC assay. The best conditions obtained for SC-CO2 extraction of flavonoids was 250 bar, 40 °C, 50 min, and with a modifier of methanol/ethanol (1:3, v/v, and that for phenolics extraction was 250 bar, 40 °C, 50 min, and with a modifier of methanol/ethanol (1:1, v/v. Meantime, flavonoids and phenolics were found to be mainly responsible for the DPPH scavenging activity of the extracts, but not for the chelating activity on ferrous ion according to Pearson correlation analysis. Furthermore, several unreported flavonoids such as apigenin, vitexin, luteolin, etc., have been detected in the extracts from A. grossedentata stems.

  10. Thermodynamic Optimization of Supercritical CO{sub 2} Brayton Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Rhim, Dong-Ryul; Park, Sung-Ho; Kim, Su-Hyun; Yeom, Choong-Sub [Institute for Advanced Engineering, Yongin (Korea, Republic of)

    2015-05-15

    The supercritical CO{sub 2} Brayton cycle has been studied for nuclear applications, mainly for one of the alternative power conversion systems of the sodium cooled fast reactor, since 1960's. Although the supercritical CO{sub 2} Brayton cycle has not been expected to show higher efficiency at lower turbine inlet temperature over the conventional steam Rankine cycle, the higher density of supercritical CO{sub 2} like a liquid in the supercritical region could reduce turbo-machinery sizes, and the potential problem of sodium-water reaction with the sodium cooled fast reactor might be solved with the use of CO{sub 2} instead of water. The supercritical CO{sub 2} recompression Brayton cycle was proposed for the better thermodynamic efficiency than for the simple supercritical CO{sub 2} Brayton cycle. Thus this paper presents the efficiencies of the supercritical CO{sub 2} recompression Brayton cycle along with several decision variables for the thermodynamic optimization of the supercritical CO{sub 2} recompression Brayton cycle. The analytic results in this study show that the system efficiency reaches its maximum value at a compressor outlet pressure of 200 bars and a recycle fraction of 30 %, and the lower minimum temperature approach at the two heat exchangers shows higher system efficiency as expected.

  11. Engineering Escherichia coli for methanol conversion.

    Science.gov (United States)

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-03-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy genes" into Escherichia coli based on in silico considerations and flux balance analysis to enable methanol dissimilation and assimilation. We determined that the most promising approach allowing the utilization of methanol was the implementation of NAD-dependent methanol dehydrogenase and the establishment of the ribulose monophosphate cycle by expressing the genes for hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloisomerase (Phi). To test for the best-performing enzymes in the heterologous host, a number of enzyme candidates from different donor organisms were selected and systematically analyzed for their in vitro and in vivo activities in E. coli. Among these, Mdh2, Hps and Phi originating from Bacillus methanolicus were found to be the most effective. Labeling experiments using (13)C methanol with E. coli producing these enzymes showed up to 40% incorporation of methanol into central metabolites. The presence of the endogenous glutathione-dependent formaldehyde oxidation pathway of E. coli did not adversely affect the methanol conversion rate. Taken together, the results of this study represent a major advancement towards establishing synthetic methylotrophs by gene transfer.

  12. Micronization of Griseofulvin by Ress in Supercritical CO2 with Cosolvent Acetone

    Institute of Scientific and Technical Information of China (English)

    胡国勤; 陈鸿雁; 蔡建国; 邓修

    2003-01-01

    Griseofulvin (GF) is an antifungal drug whose pharmaceutical activity can be improved by reducing particle size. In this study the rapid expansion of supercritical solution (RESS) was employed to micronize GF.Carbon dioxide with cosolvent acetone was chosen as a supercritical mixed solvent. The solubility of GF in super-critical CO2 with cosolvent acetone was measured using a dynamic apparatus at pressures between 12 and 32 MPa,temperatures at 313, 323 and 333 K and cosolvent concentration at 1.5, 3.0, 4.5 and 6.0% (by mole). The effect of pre-expansion pressure, extraction temperature, spraying distance, nozzle size and concentration of cosolvent on the precipitated particles was investigated. The results show that the mean particle size of griseofulvin precipitated by RESS was less than 1.2μm. An increase in pre-expansion pressure, extraction temperature, spraying distance and concentration of cosolvent resulted in a decrease in particle size under the operating condition studied. With the decrease of nozzle diameter the particle size reduces. The crystallinity and melting point of the original material and the processed particle by RESS were tested by X-ray diffraction (XRD) and differential scanning calorimetry (DSC).No evident modification in the crystal habit was found under the experimental conditions tested. The morphology of particles precipitated was analyzed bY scanning electron microscopy (SEM).

  13. Introduction to supercritical fluids a spreadsheet-based approach

    CERN Document Server

    Smith, Richard; Peters, Cor

    2013-01-01

    This text provides an introduction to supercritical fluids with easy-to-use Excel spreadsheets suitable for both specialized-discipline (chemistry or chemical engineering student) and mixed-discipline (engineering/economic student) classes. Each chapter contains worked examples, tip boxes and end-of-the-chapter problems and projects. Part I covers web-based chemical information resources, applications and simplified theory presented in a way that allows students of all disciplines to delve into the properties of supercritical fluids and to design energy, extraction and materials formation systems for real-world processes that use supercritical water or supercritical carbon dioxide. Part II takes a practical approach and addresses the thermodynamic framework, equations of state, fluid phase equilibria, heat and mass transfer, chemical equilibria and reaction kinetics of supercritical fluids. Spreadsheets are arranged as Visual Basic for Applications (VBA) functions and macros that are completely (source code) ...

  14. Mechanistical Studies on the Irradiation of Methanol in Extraterrestrial Ices

    Science.gov (United States)

    Bennett, Chris J.; Chen, Shih-Hua; Sun, Bing-Jian; Chang, Agnes H. H.; Kaiser, Ralf I.

    2007-05-01

    Pure ices of amorphous methanol, CH3OH(X1A'), were irradiated at 11 K by 5 keV electrons at 100 nA for 1 hr. These energetic electrons simulate electronic energy transfer processes that occur as interstellar ices, comets, and icy solar system bodies are subjected to irradiation from MeV ions and secondary electrons produced in this process. The results were analyzed quantitatively via absorption-reflection-absorption Fourier transform infrared (FTIR) spectroscopy, with the identification of new species aided by high-level electronic structure calculations. The unimolecular decomposition of methanol was found to proceed via the formation of (1) the hydroxymethyl radical, CH2OH(X2A''), and atomic hydrogen, H(2S1/2), (2) the methoxy radical, CH3O(X2A'), plus atomic hydrogen, (3) formaldehyde, H2CO(X1A1) plus molecular hydrogen, H2(X1Σ+g), and (4) the formation of methane, CH4(X1A1), together with atomic oxygen, O(1D). The accessibility of the last channel indicates that the reverse process, oxygen addition into methane to form methanol, should also be feasible. A kinetic model is presented for the decomposition of methanol into these species, as well as the formyl radical, HCO(X2A'), and carbon monoxide, CO(X1Σ+). During the subsequent warming up of the sample, radicals previously generated within the matrix were mobilized and found to recombine to form methyl formate, CH3OCHO(X1A'), glycolaldehyde, CH2OHCHO(X1A'), and ethylene glycol, HOCH 2CH2OH(X1A). Upper limits for the production of these species by the recombination of neighboring radicals produced during irradiation as well as during the warm-up procedure are presented. The generation of these molecules by irradiation of ices in the solid state and their subsequent sublimation into the gas phase can help explain their high abundances as observed toward hot molecular cores and underlines their importance in astrobiology.

  15. Sorption phenomena of methanol on heat treated coal; Netsushori wo hodokoshita sekitan no methanol kyuchaku tokusei

    Energy Technology Data Exchange (ETDEWEB)

    Yasuda, H.; Kaiho, M.; Yamada, O.; Soneda, Y.; Kobayashi, M.; Makino, M. [National Institute for Resources and Environment, Tsukuba (Japan)

    1996-10-28

    Experiments were carried out to learn methanol sorption characteristics of heat-treated coal. When Taiheiyo coal is heat-treated at 125{degree}C, performed with a first methanol adsorption at 25{degree}C, and then desorption at 25{degree}C, a site with strong interaction with methanol and a site with relatively weak interaction are generated in test samples. A small amount of methanol remains in both sites. Then, when the methanol is desorbed at as low temperature as 70{degree}C, the methanol in the site with strong interaction remains as it has existed therein, but the methanol in the site with relatively weak interaction desorbs partially, hence the adsorption amount in a second adsorption at 25{degree}C increases. However, when desorption is performed at as high temperature as 125{degree}C, the methanol in the site with strong interaction also desorbs, resulting in increased adsorption heat in the second adsorption. The adsorption velocity drops, however. Existence of methanol in a site with strong interaction affects the adsorption velocity, but no effect is given by methanol in a site with weak interaction. 3 refs., 4 figs.

  16. Hydrogen Production from Methanol Using Corona Discharges

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Hydrogen production at room temperature from liquid methanol has been conductedusing corona discharge. The content of water in methanol solution has a significant effect on thisproduction. When water concentration increases from 1.0 % to 16.7 %, the methanol conversionrate changes from 0.196 to 0.284 mol/h. An important finding in this investigation is theformation of ethylene glycol as a major by-product. The yield of ethylene glycol is ranged from0.0045 to 0.0075 mol/h based on the water content.

  17. Novel Anode Catalyst for Direct Methanol Fuel Cells

    Directory of Open Access Journals (Sweden)

    S. Basri

    2014-01-01

    Full Text Available PtRu catalyst is a promising anodic catalyst for direct methanol fuel cells (DMFCs but the slow reaction kinetics reduce the performance of DMFCs. Therefore, this study attempts to improve the performance of PtRu catalysts by adding nickel (Ni and iron (Fe. Multiwalled carbon nanotubes (MWCNTs are used to increase the active area of the catalyst and to improve the catalyst performance. Electrochemical analysis techniques, such as energy dispersive X-ray spectrometry (EDX, X-ray diffraction (XRD, field emission scanning electron microscopy (FESEM, and X-ray photoelectron spectroscopy (XPS, are used to characterize the kinetic parameters of the hybrid catalyst. Cyclic voltammetry (CV is used to investigate the effects of adding Fe and Ni to the catalyst on the reaction kinetics. Additionally, chronoamperometry (CA tests were conducted to study the long-term performance of the catalyst for catalyzing the methanol oxidation reaction (MOR. The binding energies of the reactants and products are compared to determine the kinetics and potential surface energy for methanol oxidation. The FESEM analysis results indicate that well-dispersed nanoscale (2–5 nm PtRu particles are formed on the MWCNTs. Finally, PtRuFeNi/MWCNT improves the reaction kinetics of anode catalysts for DMFCs and obtains a mass current of 31 A g−1 catalyst.

  18. Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction

    Directory of Open Access Journals (Sweden)

    Saravana Periaswamy Sivagnanam

    2015-05-01

    Full Text Available The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri was extracted by using environmentally friendly supercritical CO2 (SC-CO2 with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v. The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone–methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process.

  19. Biological Properties of Fucoxanthin in Oil Recovered from Two Brown Seaweeds Using Supercritical CO2 Extraction.

    Science.gov (United States)

    Sivagnanam, Saravana Periaswamy; Yin, Shipeng; Choi, Jae Hyung; Park, Yong Beom; Woo, Hee Chul; Chun, Byung Soo

    2015-05-29

    The bioactive materials in brown seaweeds hold great interest for developing new drugs and healthy foods. The oil content in brown seaweeds (Saccharina japonica and Sargassum horneri) was extracted by using environmentally friendly supercritical CO2 (SC-CO2) with ethanol as a co-solvent in a semi-batch flow extraction process and compared the results with a conventional extraction process using hexane, ethanol, and acetone mixed with methanol (1:1, v/v). The SC-CO2 method was used at a temperature of 45 °C and pressure of 250 bar. The flow rate of CO2 (27 g/min) was constant for the entire extraction period of 2 h. The obtained oil from the brown seaweeds was analyzed to determine their valuable compounds such as fatty acids, phenolic compounds, fucoxanthin and biological properties including antioxidant, antimicrobial, and antihypertension effects. The amounts of fucoxanthin extracted from the SC-CO2 oils of S. japonica and S. horneri were 0.41 ± 0.05 and 0.77 ± 0.07 mg/g, respectively. High antihypertensive activity was detected when using mixed acetone and methanol, whereas the phenolic content and antioxidant property were higher in the oil extracted by SC-CO2. The acetone-methanol mix extracts exhibited better antimicrobial activities than those obtained by other means. Thus, the SC-CO2 extraction process appears to be a good method for obtaining valuable compounds from both brown seaweeds, and showed stronger biological activity than that obtained by the conventional extraction process.

  20. Design of a stable and methanol resistant membrane with cross-linked multilayered polyelectrolyte complexes for direct methanol fuel cells

    Science.gov (United States)

    Wang, Jing; Zhao, Chengji; Lin, Haidan; Zhang, Gang; Zhang, Yang; Ni, Jing; Ma, Wenjia; Na, Hui

    Sulfonated poly (arylene ether ketone) bearing carboxyl groups (SPAEK-C) membranes have been prepared as proton exchange membranes for applications in direct methanol fuel cells (DMFCs). Multilayered polyelectrolyte complexes (PECs) which applied as methanol barrier agents are prepared by alternate deposition of the oppositely charged amino-containing poly (ether ether ketone) (Am-PEEK) and the highly sulfonated SPAEK-C via a layer-by-layer method. The cross-linked PEC (c-PEC) is derived from a simple heat-induced cross-linking reaction between Am-PEEK and SPAEK-C. Fourier transform infrared spectroscopy confirms that Am-PEEK and SPAEK-C are assembled successfully in the multilayers. The morphology of the membranes is studied by scanning electron microscopy, which shows the presence of the thin layers coated on the SPAEK-C membrane. After PEC and c-PEC modification, the methanol permeability decreases obviously when compared to that of the pristine membrane. Notably, improved proton conductivities are obtained for the PEC modified membranes in comparison with the pristine membrane. Moreover, the selectivity of these modified membranes is one order of magnitude higher than that of Nafion 117. The thermal stability, oxidative stability, water uptake and swelling of PEC and c-PEC modified membranes are also investigated.

  1. The Catalysis of NAD+ on Methanol Anode Oxidation Electrode for Direct Methanol Fuel Cell

    Institute of Scientific and Technical Information of China (English)

    ZHANG Ping; PAN Mu; YUAN Run-zhang

    2004-01-01

    A tentative idea of developing a liquid-catalytic system on methanol anode oxidation was proposed by analyzing the characteristics of methanol anode oxidation in direct methanol fuel cell. The kinetics of methanol oxidation at a glassy carbon electrode in the presence of nicotinamide adenine dinucleotide (NAD+) was investigated. It is found that the current density of methanol oxidation increases greatly and the electrochemical reaction impedance reduces obviously in the presence of NAD+ compared with those in the absence of NAD+. The catalytic activity of NAD+ is sensitive to temperature. When the temperature preponderates over 45℃, NAD+ is out of function of catalysis for methanol oxidation, which is probably due to the denaturation of NAD+ at a relatively high temperature.

  2. Supercritical fluids: Reactions, materials and applications

    Energy Technology Data Exchange (ETDEWEB)

    Tumas, W.; Jacobson, G.B.; Josephsohn, N.S.; Brown, G.H.

    1999-04-09

    A number of important processes utilizing supercritical fluids have been either implemented or are emerging for extractions, separations and a wide range of cleaning applications. Supercritical fluids can be reasonable solvents yet share many of the advantages of gases including miscibility with other gases (i.e. hydrogen and oxygen), low viscosities and high diffusivities. Carbon dioxide has the further advantages of being nontoxic, nonflammable, inexpensive and currently unregulated. The use of compressed gases, either as liquids or supercritical fluids, as reaction media offers the opportunity to replace conventional hazardous solvents and also to optimize and potentially control the effect of solvent on chemical and material processing. The last several years has seen a significant growth in advances in chemical synthesis, catalytic transformations and materials synthesis and processing. The authors report on results from an exploratory program at Los Alamos National Laboratory aimed at investigating the use of dense phase fluids, particularly carbon dioxide, as reaction media for homogeneous, heterogeneous and phase-separable catalytic reactions in an effort to develop new, environmentally-friendly methods for chemical synthesis and processing. This approach offers the possibility of opening up substantially different chemical pathways, increasing selectivity at higher reaction rates, facilitating downstream separations and mitigating the need for hazardous solvents. Developing and understanding chemical and catalytic transformations in carbon dioxide could lead to greener chemistry at three levels: (1) Solvent replacement; (2) Better chemistry (e.g. higher reactivity, selectivity, less energy consumption); and (3) New chemistry (e.g. novel separations, use of COP{sub 2} as a C-1 source).

  3. Supercritical Water Oxidation Data Acquisition Testing

    Energy Technology Data Exchange (ETDEWEB)

    K. M. Garcia

    1996-08-01

    Supercritical Water Oxidation (SCWO) is a high pressure oxidation process that blends air, water, and organic waste material in an oxidizer in which where the temperature and pressure in the oxidizer are maintained above the critical point of water. Supercritical water mixed with hydrocarbons, which would be insoluble at subcritical conditions, forms a homogeneous phase which possesses properties associated with both a gas and a liquid. Hydrocarbons in contact with oxygen and SCW are readily oxidized. These properties of SCW make it an attractive means for the destruction of waste streams containing organic materials. SCWO technology holds great promise for treating mixed wastes in an environmentally safe and efficient manner. In the spring of 1994 the U.S. Department of Energy (DOE) initiated a Supercritical Water Oxidation Data Acquisition Testing (SCWODAT) program. The SCWODAT program provided further information and operational data on the effectiveness of treating both simulated mixed waste and typical Navy hazardous waste using the SCWO technology. The program concentrated on the acquisition of data through pilot plant testing. The Phase I DOE testing used a simulated waste stream that contained a complex machine cutting oil and metals, that acted as surrogates for radionuclides. The Phase II Navy testing included pilot testing using hazardous waste materials to demonstrate the effectiveness of the SCWO technology. The SCWODAT program demonstrated that the SCWO process oxidized the simulated waste stream containing complex machine cutting oil, selected by DOE as representative of one of the most difficult of the organic waste streams for which SCWO had been applied. The simulated waste stream with surrogate metals in solution was oxidized, with a high destruction efficiency, on the order of 99.97%, in both the neutralized and unneutralized modes of operation.

  4. Methanol production from fermentor off-gases

    Science.gov (United States)

    Dale, B. E.; Moreira, A. R.

    The off gases from an acetone butanol fermentation facility are composed mainly of CO2 and H2. Such a gas stream is an ideal candidate as a feed to a methanol synthesis plant utilizing modern technology recently developed and known as the CDH-methanol process. A detailed economic analysis for the incremental cost of a methanol synthesis plant utilizing the off gases from an acetone butanol fermentation indicates a profitable rate of return of 25 to 30% under the most likely production conditions. Bench scale studies at different fermentor mixing rates indicate that the volume of gases released during the fermentation is a strong function of the agitation rate and point to a potential interaction between the volume of H2 evolved and the levels of butanol present in the final fermented broth. Such interaction may require establishing optimum operating conditions for an integrated butanol fermentation methanol synthesis plant.

  5. Methanol: A Versatile Fuel for Immediate Use

    Science.gov (United States)

    Reed, T. B.; Lerner, R. M.

    1973-01-01

    Advocates the large-scale production and use of methanol as a substitute for the diminishing reserves of low-cost petroleum resources. Describes the manufacturing process and advantages of the versatile fuel. (JR)

  6. Quiet Changes in the Methanol Supply Mode

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    @@ The coal chemicals sector, the new coal chemicals sector in particular, has been emerging fast in China in recent years. The production scale of methanol as an important coal chemical product has expanded constantly.

  7. Cancer chemopreventive property of Bidens pilosa methanolic ...

    African Journals Online (AJOL)

    admin

    Cancer chemopreventive property of Bidens pilosa methanolic extract on two stage in vivo skin carcinogenesis ... In the forestomach, kidney and lung, glutathione S-transferase and ..... weight gain profile or terminal in mice treated with the two ...

  8. Ab initio molecular dynamics study of liquid methanol

    CERN Document Server

    Handgraaf, J W; Meijer, E J; Handgraaf, Jan-Willem; Erp, Titus S. van; Meijer, Evert Jan

    2003-01-01

    We present a density-functional theory based molecular-dynamics study of the structural, dynamical, and electronic properties of liquid methanol under ambient conditions. The calculated radial distribution functions involving the oxygen and hydroxyl hydrogen show a pronounced hydrogen bonding and compare well with recent neutron diffraction data, except for an underestimate of the oxygen-oxygen correlation. We observe that, in line with infrared spectroscopic data, the hydroxyl stretching mode is significantly red-shifted in the liquid. A substantial enhancement of the dipole moment is accompanied by significant fluctuations due to thermal motion. Our results provide valuable data for improvement of empirical potentials.

  9. Supercritical fluid thermodynamics from equations of state

    Science.gov (United States)

    Giovangigli, Vincent; Matuszewski, Lionel

    2012-03-01

    Supercritical multicomponent fluid thermodynamics are often built from equations of state. We investigate mathematically such a construction of a Gibbsian thermodynamics compatible at low density with that of ideal gas mixtures starting from a pressure law. We further study the structure of chemical production rates obtained from nonequilibrium statistical thermodynamics. As a typical application, we consider the Soave-Redlich-Kwong cubic equation of state and investigate mathematically the corresponding thermodynamics. This thermodynamics is then used to study the stability of H2-O2-N2 mixtures at high pressure and low temperature as well as to illustrate the role of nonidealities in a transcritical H2-O2-N2 flame.

  10. Supercritical-pressure light water cooled reactors

    CERN Document Server

    Oka, Yoshiaki

    2014-01-01

    This book focuses on the latest reactor concepts, single pass core and experimental findings in thermal hydraulics, materials, corrosion, and water chemistry. It highlights research on supercritical-pressure light water cooled reactors (SCWRs), one of the Generation IV reactors that are studied around the world. This book includes cladding material development and experimental findings on heat transfer, corrosion and water chemistry. The work presented here will help readers to understand the fundamental elements of reactor design and analysis methods, thermal hydraulics, materials and water

  11. Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol–methanol mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Martinez-Guerra, Edith; Gude, Veera Gnaneswar, E-mail: gude@cee.msstate.edu

    2014-12-15

    Highlights: • Pulse sonication effect on transesterification of waste vegetable oil was studied. • Effects of ethanol, methanol, and alcohol mixtures on FAMEs yield were evaluated. • Effect of ultrasonic intensity, power density, and its output rates were evaluated. • Alcohol mixtures resulted in higher biodiesel yields due to better solubility. - Abstract: This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol–methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol–methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1–2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol–methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.

  12. Vacuum-Ultraviolet (VUV) Photoionization of Small Methanol and Methanol-Water Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Kostko, Oleg; Belau, Leonid; Wilson, Kevin R.; Ahmed, Musahid

    2008-04-24

    In this work, we report on the vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuum-ultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH+(n = 1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH n(H2O)H+ (n = 2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH+, (CH3OH)2+, (CH3OH)nH+ (n = 1-9), and (CH3OH)n(H2O)H+ (n = 2-9) as a function of photon energy. With an increasein the water content in the molecular beam, there is an enhancement of photoionization intensity for the methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  13. Vacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Musahid; Ahmed, Musahid; Wilson, Kevin R.; Belau, Leonid; Kostko, Oleg

    2008-05-12

    In this work we report on thevacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuumultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

  14. Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

    Science.gov (United States)

    Zhu, Yimin; Zelenay, Piotr

    2006-03-21

    A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

  15. Microfluidic distillation chip for methanol concentration detection.

    Science.gov (United States)

    Wang, Yao-Nan; Liu, Chan-Chiung; Yang, Ruey-Jen; Ju, Wei-Jhong; Fu, Lung-Ming

    2016-03-17

    An integrated microfluidic distillation system is proposed for separating a mixed ethanol-methanol-water solution into its constituent components. The microfluidic chip is fabricated using a CO2 laser system and comprises a serpentine channel, a boiling zone, a heating zone, and a cooled collection chamber filled with de-ionized (DI) water. In the proposed device, the ethanol-methanol-water solution is injected into the microfluidic chip and driven through the serpentine channel and into the collection chamber by means of a nitrogen carrier gas. Following the distillation process, the ethanol-methanol vapor flows into the collection chamber and condenses into the DI water. The resulting solution is removed from the collection tank and reacted with a mixed indicator. Finally, the methanol concentration is inversely derived from the absorbance measurements obtained using a spectrophotometer. The experimental results show the proposed microfluidic system achieves an average methanol distillation efficiency of 97%. The practicality of the proposed device is demonstrated by detecting the methanol concentrations of two commercial fruit wines. It is shown that the measured concentration values deviate by no more than 3% from those obtained using a conventional bench top system.

  16. Class I methanol masers: Masers with EGOs

    CERN Document Server

    Chen, Xi; Shen, Zhi-Qiang

    2009-01-01

    We have compared the results of a number of published class I methanol maser surveys with the catalogue of high-mass outflow candidates identified from the GLIMPSE survey (known as extended green objects or EGOs). We find class I methanol masers associated with approximately two-thirds of EGOs. Although the association between outflows and class I methanol masers has long been postulated on the basis of detailed studies of a small number of sources, this result demonstrates the relationship for the first time on a statistical basis. Despite the publication of a number of searches for class I methanol masers, a close physical association with another astrophysical object which could be targeted for the search is still lacking. The close association between class I methanol masers and EGOs therefore provides a large catalogue of candidate sources, most of which have not previously been searched for class I methanol masers. Interstellar masers and outflows have both been proposed to trace an evolutionary sequenc...

  17. Modelling and experimental studies on a direct methanol fuel cell working under low methanol crossover and high methanol concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, V.B.; Pinto, A.M.F.R. [Centro de Estudos de Fenomenos de Transporte, Departamento de Eng. Quimica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto (Portugal); Rangel, C.M. [Instituto Nacional de Energia e Geologia, Fuel Cells and Hydrogen, Estrada do Paco do Lumiar, 1649-038 Lisboa (Portugal)

    2009-08-15

    A number of issues need to be resolved before DMFC can be commercially viable such as the methanol crossover and water crossover which must be minimised in portable DMFCs. The main gain of this work is to systematically vary commercial MEA materials and check their influence on the cell performance of a direct methanol fuel cell operating at close to room temperature. A detailed experimental study on the performance of an <> developed DMFC with 25 cm{sup 2} of active membrane area, working near the ambient conditions is described. Tailored MEAs (membrane-electrode assemblies), with different structures and combinations of gas diffusion layers (GDLs), were designed and tested in order to select optimal working conditions at high methanol concentration levels without sacrificing performance. The experimental polarization and power density curves were successfully compared with the predictions of a steady state, one-dimensional model accounting for coupled heat and mass transfer, along with the electrochemical reactions occurring in the DMFC recently developed by the same authors. The influence of the anode gas diffusion layer media, the membrane thickness and the MEA properties on the cell performance are explained under the light of the predicted methanol crossover rate across the membrane. A tailored MEA build-up with the common available commercial materials was proposed to achieve relatively low methanol crossover, operating at high methanol concentrations. The use of adequate materials for the gas diffusion layers (carbon paper at the anode GDL and carbon cloth at the cathode GDL) enables the use of thinner membranes enhancing the water back diffusion which is essential to work at high methanol concentrations. (author)

  18. Preparation of Semi-interpenetrating Polymer Network of Silicon Rubber and Poly(methyl methylacrylate) Using Supercritical CO2

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    The heterogeneous free-radical polymerization of methyl methylacrylatc (MMA) and divinylbenzene (DVB) as cross-linker within supercritical carbon dioxide-swollen silicon rubber (SR) has been studied as an approach to preparing semi-interpenetrating polymer network (semi IPN) of SR and poly(methyl methylacrylate) (PMMA). The SR/PMMA semi-IPNs were characterized by scanning electron microscopy (SEM) and dynamic mechanical analyzer (DMA).

  19. Preparation of Semi—interpenetrating Polymer Network of Silicon Rubber and Poly (methyl methylacrylate) Using Supercritical CO2

    Institute of Scientific and Technical Information of China (English)

    ZhiMinLIU; JiaQiuWANG; 等

    2002-01-01

    The heterogeneous free-radical polymerization of methyl methylacrylate(MMA) and divinylbenzene (DVB) as cross-linker within supercritical carbon dioxide-swollen silicon rubber (SR) has been studied as an approach to preparing semi-interpenetrating polymer network (semi-IPN) of SR and poly(methyl methylacrylate)(PMMA). The SR/PMMA semi-IPNs were characterized by scanning electron microscopy(SEM) and dynamic mechanical analyzer (DMA).

  20. Supercritical impregnation of polymer matrices spatially confined in microcontainers for oral drug delivery: Effect of temperature, pressure and time

    DEFF Research Database (Denmark)

    Marizza, Paolo; Pontoni, L.; Rindzevicius, Tomas

    2016-01-01

    parameters(temperature, pressure, time, drug concentration in the supercritical phase) was elucidated with respectto the loading capacity. The microcontainer filling was observed by means of optical macroimaging, X-ray microtomography and scanning electron microscopy. The physical state of the drug...... described. The drug loading can be controlled with high accuracy and reproducibility andthe impregnated drug is in amorphous state. These results demonstrate that SCI can be used as a highthroughput loading technique for microfabricated devices for oral drug delivery....

  1. Effects of supercritical environment on hydrocarbon-fuel injection

    Science.gov (United States)

    Shin, Bongchul; Kim, Dohun; Son, Min; Koo, Jaye

    2017-04-01

    In this study, the effects of environment conditions on decane were investigated. Decane was injected in subcritical and supercritical ambient conditions. The visualization chamber was pressurized to 1.68 MPa by using nitrogen gas at a temperature of 653 K for subcritical ambient conditions. For supercritical ambient conditions, the visualization chamber was pressurized to 2.52 MPa by using helium at a temperature of 653 K. The decane injection in the pressurized chamber was visualized via a shadowgraph technique and gradient images were obtained by a post processing method. A large variation in density gradient was observed at jet interface in the case of subcritical injection in subcritical ambient conditions. Conversely, for supercritical injection in supercritical ambient conditions, a small density gradient was observed at the jet interface. In a manner similar to that observed in other cases, supercritical injection in subcritical ambient conditions differed from supercritical ambient conditions such as sphere shape liquid. Additionally, there were changes in the interface, and the supercritical injection core width was thicker than that in the subcritical injection. Furthermore, in cases with the same injection conditions, the change in the supercritical ambient normalized core width was smaller than the change in the subcritical ambient normalized core width owing to high specific heat at the supercritical injection and small phase change at the interface. Therefore, the interface was affected by the changing ambient condition. Given that the effect of changing the thermodynamic properties of propellants could be essential for a variable thrust rocket engine, the effects of the ambient conditions were investigated experimentally.

  2. Sterion membranes in Direct Methanol fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Linares, J. J.; Lobato, J.; Canizares, P.; Rodrigo, M. A.; Fernandez, A.

    2005-07-01

    Direct Methanol Fuel Cells (DMFCs) has been postulated as an alternative to traditional hydrogen fed Polymer Electrolyte Membrane Fuel Cells (H2-PEMFCs). Among their advantages, it can be pointed out the low cost of the fuel, simplicity of design, large availability, easy handling and distribution. However, there are still some challenges in this field, such as the development of electrocatalysts which can enhance the electrokinetics of methanol oxidation, the discovery of an electrolyte membrane with high conductivity and low methanol crossover at the same time and the production of methanol-tolerant electrocatalysts with high activity for oxygen reduction. So far, Nafion 117 has been the polymer membrane most widely used in DMFCs. Yet, it is well known that Nafion (Du Pont Inc.) membranes are not good barrier for methanol, so that the coulombic efficiency of Nafion-based DMFCs is significantly reduced by the chemical oxidation of methanol in the cathode. Recently, a new perfluorinated polymer with sulphonic acid groups (PFSA) has been developed, under the commercial name of Sterion (David Fuel Cell Components). As a difference as opposed to Nafion, this membrane is cast by the solution casting method, which provides a different sulphonic cluster configuration as compared to the extrusion cast Nafion membranes, which may give rise to different methanol crossover behaviour. In this work, it has been studied and analysed the suitability of Sterion in the DMFCs field. For that, it has been measured the methanol permeability of this membrane at different solute concentration and temperature, and its performance in an actual fuel cell at different operational conditions, such as methanol concentration, temperature and back pressure. Tests have been made using both oxygen and air in the cathode and half-cell potentials have been evaluated in some measurements in order to discriminate the contribution of both semi-reactions to the overall cell overvoltage. A lifetime

  3. Production of methanol/DME from biomass

    Energy Technology Data Exchange (ETDEWEB)

    Ahrenfeldt, J.; Birk Henriksen, U.; Muenster-Swendsen, J.; Fink, A.; Roengaard Clausen, L.; Munkholt Christensen, J.; Qin, K.; Lin, W.; Arendt Jensen, P.; Degn Jensen, A.

    2011-07-01

    In this project the production of DME/methanol from biomass has been investigated. Production of DME/methanol from biomass requires the use of a gasifier to transform the solid fuel to a synthesis gas (syngas) - this syngas can then be catalytically converted to DME/methanol. Two different gasifier types have been investigated in this project: 1) The Two-Stage Gasifier (Viking Gasifier), designed to produce a very clean gas to be used in a gas engine, has been connected to a lab-scale methanol plant, to prove that the gas from the gasifier could be used for methanol production with a minimum of gas cleaning. This was proved by experiments. Thermodynamic computer models of DME and methanol plants based on using the Two-Stage Gasification concept were created to show the potential of such plants. The models showed that the potential biomass to DME/methanol + net electricity energy efficiency was 51-58% (LHV). By using waste heat from the plants for district heating, the total energy efficiencies could reach 87-88% (LHV). 2) A lab-scale electrically heated entrained flow gasifier has been used to gasify wood and straw. Entrained flow gasifiers are today the preferred gasifier type for commercial coal gasification, but little information exists on using these types of gasifiers for biomass gasification. The experiments performed provided quantitative data on product and gas composition as a function of operation conditions. Biomass can be gasified with less oxygen consumption compared to coal. The organic fraction of the biomass that is not converted to gas appears as soot. Thermodynamic computer models of DME and methanol plants based on using entrained flow gasification were created to show the potential of such plants. These models showed that the potential torrefied biomass to DME/methanol + net electricity energy efficiency was 65-71% (LHV). Different routes to produce liquid transport fuels from biomass are possible. They include production of RME (rapeseed oil

  4. In-Situ Synchrotron Radiation Study of Formation and Growth of Crystalline CexZr1-xO2 Nanoparticles Synthesized in Supercritical Water

    DEFF Research Database (Denmark)

    Tyrsted, Christoffer; Becker-Christensen, Jacob; Hald, Peter

    2010-01-01

    -zirconia system, the growth of ceria and zirconia nanoparticles is fundamentally different under supercritical water conditions. For comparison, ex situ synthesis has also been performed using an in-house supercritical flow reactor. The resulting samples were analyzed using PXRD, small-angle X-ray scattering...... (SAXS), and transmission electron microscopy (TEM). The nanoparticles with x= 0, 0.2, and 0.5 have very low polydispersities. The sizes range from 4 nm to 7 nm, and the particles exhibit a reversibly pH-dependent agglomeration. Udgivelsesdato: 2010......In situ synchrotron powder X-ray diffraction (PXRD) measurements have been conducted to follow the nucleation and growth of crystalline CexZr1-xO2 nanoparticles synthesized in supercritical water with a full substitution variation (x = 0, 0.2, 0.5, 0.8, and 1.0). Direction-dependent growth curves...

  5. Supercritical Fluid Extraction: Present Status and Prospects

    Energy Technology Data Exchange (ETDEWEB)

    King, J. W.

    2002-07-01

    Supercritical extraction (SFE), using primarily environmentally-benign carbon dioxide (CO{sub 2}) as the extraction agent, is reviewed with respect to its present status and future use. SFE was developed for analytical application in the mid 1980's in response to the desire to reduce the use of organic solvents in the laboratory environment and is becoming a standard method for the preparation and analysis of lipid-containing sample matrices. Currently, analytical SFE is predominately practiced in the off-line mode, using both sequential and parallel extraction modes. Depending on the instrumental configuration, the preparation of up to 24 samples can be accomplished on one instrument on a daily basis. Several other benefits can be achieved using SFE, such as the processing of thermally-sensitive analytes and rapid analyte extraction kinetics relative to extraction with liquid solvents. Examples are provided not only of the analytical SFE of oils and fats, but of volatile solutes from an array of sample types. Finally, the relevance of analytical SFE to processing with supercritical fluids (SFs) is documented using examples from our own research involving a combinatorial approach to optimising processing conditions. (Author) 70 refs.

  6. Supercritical extraction of oleaginous: parametric sensitivity analysis

    Directory of Open Access Journals (Sweden)

    Santos M.M.

    2000-01-01

    Full Text Available The economy has become universal and competitive, thus the industries of vegetable oil extraction must advance in the sense of minimising production costs and, at the same time, generating products that obey more rigorous patterns of quality, including solutions that do not damage the environment. The conventional oilseed processing uses hexane as solvent. However, this solvent is toxic and highly flammable. Thus the search of substitutes for hexane in oleaginous extraction process has increased in the last years. The supercritical carbon dioxide is a potential substitute for hexane, but it is necessary more detailed studies to understand the phenomena taking place in such process. Thus, in this work a diffusive model for semi-continuous (batch for the solids and continuous for the solvent isothermal and isobaric extraction process using supercritical carbon dioxide is presented and submitted to a parametric sensitivity analysis by means of a factorial design in two levels. The model parameters were disturbed and their main effects analysed, so that it is possible to propose strategies for high performance operation.

  7. Supercritical fluid chromatography (SFC). Pt. 3. Applications

    Energy Technology Data Exchange (ETDEWEB)

    Leyendecker, D.; Hoefler, F.

    1989-05-01

    During the last few years, Supercritical Fluid Chromatography (SFC) has been emerged from an academic object of research to an important tool for the analytical chemist. Persuasive SFC-applications have been reported analyzing substrates with low volatilities, either due to high molecular weights or to high polarities, thermally or solvatolytically labile molecules, or analytes without chromophores or electroactive groups. Examples are oligomers and polymers up to a molecular weight of 10,000 g/mol, e.g., polysiloxanes, polyethers (nonionic surfactants), polyesters, polystyrenes and other vinyl polymers, polyenes etc. In addition, SFC is applicable to the analysis of several monomers. In the petroleum and coal industries, SFC was employed for the characterization of high boiling hydrocarbon mixtures as well as for group separations of alkanes, olefins, and aromatics. Due to the high solvent strength of supercritical fluids, several pesticides, herbicides, and fungicides can be determined either separately or in combination with polar metabolites. Physiologically active substances often are thermally labile and polar at the same time. SFC has been successfully applied to the analysis of steroids, prostaglandins, cannabinoids and other drugs, flavours, and medicines. It is also well suited for analyzing natural or synthetic mono-, di-, and triglycerides. (orig.).

  8. Toward Better Modeling of Supercritical Turbulent Mixing

    Science.gov (United States)

    Selle, Laurent; Okongo'o, Nora; Bellan, Josette; Harstad, Kenneth

    2008-01-01

    study was done as part of an effort to develop computational models representing turbulent mixing under thermodynamic supercritical (here, high pressure) conditions. The question was whether the large-eddy simulation (LES) approach, developed previously for atmospheric-pressure compressible-perfect-gas and incompressible flows, can be extended to real-gas non-ideal (including supercritical) fluid mixtures. [In LES, the governing equations are approximated such that the flow field is spatially filtered and subgrid-scale (SGS) phenomena are represented by models.] The study included analyses of results from direct numerical simulation (DNS) of several such mixing layers based on the Navier-Stokes, total-energy, and conservation- of-chemical-species governing equations. Comparison of LES and DNS results revealed the need to augment the atmospheric- pressure LES equations with additional SGS momentum and energy terms. These new terms are the direct result of high-density-gradient-magnitude regions found in the DNS and observed experimentally under fully turbulent flow conditions. A model has been derived for the new term in the momentum equation and was found to perform well at small filter size but to deteriorate with increasing filter size. Several alternative models were derived for the new SGS term in the energy equation that would need further investigations to determine if they are too computationally intensive in LES.

  9. Supercritical water oxidation treatment of textile sludge.

    Science.gov (United States)

    Zhang, Jie; Wang, Shuzhong; Li, Yanhui; Lu, Jinling; Chen, Senlin; Luo, XingQi

    2016-10-17

    In this work, we studied the supercritical water oxidation (SCWO) of the textile sludge, the hydrothermal conversion of typical textile compounds and the corrosion properties of stainless steel 316. Moreover, the influence mechanisms of NaOH during these related processes were explored. The results show that decomposition efficiency for organic matter in liquid phase of the textile sludge was improved with the increment of reaction temperature or oxidation coefficient. However, the organic substance in solid phase can be oxidized completely in supercritical water. Serious coking occurred during the high pressure water at 250-450°C for the Reactive Orange 7, while at 300 and 350°C for the polyvinyl alcohol. The addition of NaOH not only accelerated the destruction of organic contaminants in the SCWO reactor, but effectively inhibited the dehydration conversion of textile compounds during the preheating process, which was favorable for the treatment system of textile sludge. The corrosion experiment results indicate that the stainless steel 316 could be competent for the body materials of the reactor and the heat exchangers. Furthermore, there was prominent enhancement of sodium hydroxide for the corrosion resistance of 316 in subcritical water. On the contrary the effect was almost none during SCWO.

  10. Supercritical Fluid Extraction of Palm Carotenoids

    Directory of Open Access Journals (Sweden)

    Puah C. Wei

    2005-01-01

    Full Text Available The extraction of carotenoids from crude palm oil was carried out in a dynamic (flow- through supercritical fluid extraction system. The carotenoids obtained were quantified using off-line UV-visible spectrophotometry. The effects of operating pressure and temperature, flow rate of the supercritical carbon dioxide (SC-CO2, sample size of feed used on the solubility of palm carotenoids were investigated. The results showed that the extraction of carotenoids was governed by its solubility in the SC-CO2 and can be enhanced by increasing pressure at a constant temperature or decreasing temperature at a constant pressure. Increasing the flow rate and decreasing the sample size can reduce the extraction time but do not enhance the solubility. Palm carotenoids have very low solubility in SC-CO2 in the range of 1.31 x 10-4 g kg-1 to 1.58 x 10-3 g kg-1 for the conditions investigated in this study. The experimental data obtained were compared with those published by other workers and correlated by a density-based equation as proposed by Chrastil.

  11. Desorption of toluene from modified clays using supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    Carneiro D. G. P.

    2004-01-01

    Full Text Available The main objective of this work is to study the regeneration capacity of modified clays using supercritical fluid. These modified clays are used as organic compound adsorvents. The experimental step was done using a packed column with the clay contaminated by toluene. The results obtained showed the influence of the density of the supercritical CO2 and of the organic modifier in the desorption process. These data were modeled with first- and second-order models. Better results were obtained using the second-order model. This study makes possible the scale-up of the desorption process for regeneration of solid matrices using supercritical fluids.

  12. High Density Thermal Energy Storage with Supercritical Fluids

    Science.gov (United States)

    Ganapathi, Gani B.; Wirz, Richard

    2012-01-01

    A novel approach to storing thermal energy with supercritical fluids is being investigated, which if successful, promises to transform the way thermal energy is captured and utilized. The use of supercritical fluids allows cost-affordable high-density storage with a combination of latent heat and sensible heat in the two-phase as well as the supercritical state. This technology will enhance penetration of several thermal power generation applications and high temperature water for commercial use if the overall cost of the technology can be demonstrated to be lower than the current state-of-the-art molten salt using sodium nitrate and potassium nitrate eutectic mixtures.

  13. Effect of pressure of supercritical carbon dioxide on morphology of wool fibers during dyeing process

    Directory of Open Access Journals (Sweden)

    Zheng Lai-Jiu

    2015-01-01

    Full Text Available In this paper, the effect of pressure release rate on dyeing of wool fibers was studied in the supercritical carbon dioxide dyeing. Surface morphology, chemical composition and color difference at different pressure release rates were investigated by employing scanning electron microscope, color matching, and measuring instrument. Experiment data reveal that wool fibers are easy to be damaged with increasing pressure release rate. Fiber’s surface brightness varies also with the pressure release rate. The phenomena are theoretically explained using Bernoulli's principle.

  14. Rapid Production of Micro- and Nano-particles Using Supercritical Water

    CERN Document Server

    Fang, Zhen

    2010-01-01

    This book shows how to use supercritical water (SCW) to synthesize nano- and micro- oxides, inorganic salts and metal particles and its recent advancement. Also polymer/biomass particles can be produced by using the method of precipitation of solutes from SCW. The particles can be used as catalysts for biomass conversions, materials in ceramics & electronic devices and composite materials. Particles are easily produced continuously in a flow reactor in short and long reaction times. Besides the synthesis process, the book also present studies of the properties of these materials. The size, siz

  15. Electrocatalysts based on Ru nanoparticles : effect of methanol on the ORR Tafel slope

    Energy Technology Data Exchange (ETDEWEB)

    Duron-Torres, S.M.; Leyva-Noyola, F.; Galvan-Valencia, M. [Univ. Autonoma de Zacatecas, Guadalupe, Zacatecas (Mexico). U.A. de Ciencias Quimicas; Solorza-Feria, O. [Centro de Investigacion y Estudios Avanzados del I.P.N., Col. San Pedro Zacatenco (Mexico). Depto. de Quimica

    2008-04-15

    Proton Exchange Membrane Fuel Cells (PEMFCs) are promising candidates in systems that require small-sized power sources such as non-stationary electronic equipment and transportation. However, the scientific and technical challenges of PEMFC which include diminution of catalytic charges, catalyst substitution, membrane development, optimization of bipolar plates and a global cost decrease require further study. A strategic approach that will help with the diffusion and assimilation of the PEMFC technology involves the use of fuel other than hydrogen in cells such as methanol. However, the use of methanol in direct methanol fuel cells (DMFC) presents further challenges including slow kinetics in both anodic and cathodic reactions, and fuel crossover due to exchange membrane alcohol permeability, meaning a lower global efficiency of DMFC as compared with the hydrogen fuel cell. This article provided a contribution to the synthesis and characterization of novel catalytic materials research for DMFC. A series of materials based on ruthenium (Ru) nanoparticles were produced and catalytically studied in a multielectron charge transfer process. These materials are electroactive for the oxygen reduction reaction (ORR) in acid medium and methanol tolerant as well. The Ru nanoparticles and some binary and ternary mixtures with platinum (Pt) and cobalt (Co) were obtained by a pyrolysis procedure of solid precursors at 190 degrees Celsius. Physiochemical characterization was conducted by using a scanning electronic microscopy and energy dispersion spectroscopy mapping. Kinetic parameters of the cathodic reaction in a 0.5M sulfuric acid solution at different methanol concentrations were compared using electrochemical characterization with cyclic voltammetry and rotating disc electrodes. It was concluded that methanol has a major effect on the ORR electrocatalytic activity on binary Ru-Pt materials with a higher Pt proportion. In addition, the methanol effect on the Tafel slope

  16. The effect of oxygen on methanol oxidation by an obligate metahnotrophic bacterium studied by in vivo 13C nuclear magnetic resonance spectroscopy

    NARCIS (Netherlands)

    Costa, C.; Vecherskaya, M.; Dijkema, C.; Stams, A.J.M.

    2001-01-01

    13C NMR was used to study the effect of oxygen on methanol oxidation by a type II methanotrophic bacterium isolated from a bioreactor in which methane was used as electron donor for denitrification. Under high (35-25€oxygen conditions the first step of methanol oxidation to formaldehyde was much

  17. Methanol utilizing Desulfotomaculum species utilizes hydrogen in a methanol-fed sulfate-reducing bioreactor

    NARCIS (Netherlands)

    Balk, M.; Weijma, J.; Goorissen, H.P.; Ronteltap, M.; Hansen, T.A.; Stams, A.J.M.

    2007-01-01

    A sulfate-reducing bacterium, strain WW1, was isolated from a thermophilic bioreactor operated at 65 degrees C with methanol as sole energy source in the presence of sulfate. Growth of strain WW1 on methanol or acetate was inhibited at a sulfide concentration of 200 mg l(-1), while on H-2/CO2, no ap

  18. Transesterification of waste vegetable oil under pulse sonication using ethanol, methanol and ethanol-methanol mixtures.

    Science.gov (United States)

    Martinez-Guerra, Edith; Gude, Veera Gnaneswar

    2014-12-01

    This study reports on the effects of direct pulse sonication and the type of alcohol (methanol and ethanol) on the transesterification reaction of waste vegetable oil without any external heating or mechanical mixing. Biodiesel yields and optimum process conditions for the transesterification reaction involving ethanol, methanol, and ethanol-methanol mixtures were evaluated. The effects of ultrasonic power densities (by varying sample volumes), power output rates (in W), and ultrasonic intensities (by varying the reactor size) were studied for transesterification reaction with ethanol, methanol and ethanol-methanol (50%-50%) mixtures. The optimum process conditions for ethanol or methanol based transesterification reaction of waste vegetable oil were determined as: 9:1 alcohol to oil ratio, 1% wt. catalyst amount, 1-2 min reaction time at a power output rate between 75 and 150 W. It was shown that the transesterification reactions using ethanol-methanol mixtures resulted in biodiesel yields as high as >99% at lower power density and ultrasound intensity when compared to ethanol or methanol based transesterification reactions.

  19. Characterization of five chemistries and three particle sizes of stationary phases used in supercritical fluid chromatography.

    Science.gov (United States)

    Khater, S; West, C; Lesellier, E

    2013-12-06

    Sub-2-microns particles employed as supporting phases are known to favor column efficiency. Recently a set of columns based on sub-2-microns particles for use with supercritical fluid mobile phases have been introduced by Waters. Five different stationary phase chemistries are available: BEH silica, BEHEthyl-pyridine, X Select CSH Fluorophenyl, HSS C18 SB and BEH Shield RP18. This paper describes the characterization of 15 stationary phases, the five different chemistries, and three particle sizes, 1.7 (or 1.8), 3.5 and 5 microns, with the same carbon dioxide–methanol mobile phase and a set of more than a hundred compounds. The interactions established in the 15 different chromatographic systems used in supercritical fluid chromatography (SFC) are assessed with linear solvation energy relationships (LSERs).The results show the good complementarity of the five column chemistries, and their comparative location inside a classification map containing today around 70 different commercial phases. Among the five different chemistries, the HSS C18 SB phase displays a rather unusual behavior in regards of classical C18 phases, as it displays significant hydrogen–bonding interactions. Besides, it appears, as expected, that the BEH Ethyl–pyridine phase has weak interactions with basic compounds. The effect of particle size was studied because smaller particles induce increased inlet and internal pressure. For compressible fluids,this pressure change modifies the fluid density, i.e. the apparent void volume and the eluting strength.These changes could modify the retention and the selectivity of compounds in the case of method trans-fer, by using different particle sizes, from 5 down to 1.7 m. A hierarchical cluster analysis shows that stationary phase clusters were based on the phase chemistry rather than on the particle size, meaning that method transfer from 5 to 1.7 microns can be achieved in the subcritical domain i.e. by using a weakly compressible fluid.

  20. Biofuel production from palm oil with supercritical alcohols: effects of the alcohol to oil molar ratios on the biofuel chemical composition and properties.

    Science.gov (United States)

    Sawangkeaw, Ruengwit; Teeravitud, Sunsanee; Bunyakiat, Kunchana; Ngamprasertsith, Somkiat

    2011-11-01

    Biofuel production from palm oil with supercritical methanol (SCM) and supercritical ethanol (SCE) at 400 °C and 15 MPa were evaluated. At the optimal alcohol to oil molar ratios of 12:1 and 18:1 for the SCM and SCE processes, respectively, the biofuel samples were synthesized in a 1.2-L reactor and the resulting biofuel was analyzed for the key properties including those for the diesel and biodiesel standard specifications. Biofuel samples derived from both the SCM and SCE processes could be used as an alternative fuel after slight improvement in their acid value and free glycerol content. The remarkable advantages of this novel process were: the additional fuel yield of approximately of 5% and 10% for SCM and SCE, respectively; the lower energy consumption for alcohol preheating, pumping and recovering than the biodiesel production with supercritical alcohols that use a high alcohol to oil molar ratio of 42:1. Copyright © 2011 Elsevier Ltd. All rights reserved.

  1. Optimization of supercritical fluid extraction of essential oils and fatty acids from flixweed (Descurainia Sophia L.) seed using response surface methodology and central composite design.

    Science.gov (United States)

    Ara, Katayoun Mahdavi; Jowkarderis, Mina; Raofie, Farhad

    2015-07-01

    Essential oils and fatty acids of Descurainia sophia L. seed were obtained by supercritical CO2 extraction and steam distillation methods. The effect of different parameters such as pressure, temperature, modifier volume, dynamic and static extraction timeon the extraction yield were optimized using a central composite design after a 2 (n-1) fractional factorial design. The results showed that under the pressure of 355 bar, temperature of 65 °C, methanol volume of 150 μL, dynamic and static extraction times of 35 and 10 min, respectively, the major components were methyl linoleate (18.2 %), camphor (12.32 %), cis-thujone (11.3 %) and trans-caryophyllene (9.17 %). The results indicated that by using the proper conditions, the supercritical fluid extraction is more selective than the steam distillation method. Extraction yields based on supercritical fluid extraction varied in the range of 0.68 to 17.1 % (w/w), and the extraction yield based on the steam distillation was 0.25 % (v/w).

  2. Observations of Electromagnetic Whistler Precursors at Supercritical Interplanetary Shocks

    Science.gov (United States)

    Wilson, L. B., III; Koval, A.; Szabo, Adam; Breneman, A.; Cattell, C. A.; Goetz, K.; Kellogg, P. J.; Kersten, K.; Kasper, J. C.; Maruca, B. A.; Pulupa, M.

    2012-01-01

    We present observations of electromagnetic precursor waves, identified as whistler mode waves, at supercritical interplanetary shocks using the Wind search coil magnetometer. The precursors propagate obliquely with respect to the local magnetic field, shock normal vector, solar wind velocity, and they are not phase standing structures. All are right-hand polarized with respect to the magnetic field (spacecraft frame), and all but one are right-hand polarized with respect to the shock normal vector in the normal incidence frame. They have rest frame frequencies f(sub ci) < f much < f(sub ce) and wave numbers 0.02 approx < k rho (sub ce) approx <. 5.0. Particle distributions show signatures of specularly reflected gyrating ions, which may be a source of free energy for the observed modes. In one event, we simultaneously observe perpendicular ion heating and parallel electron acceleration, consistent with wave heating/acceleration due to these waves. Al though the precursors can have delta B/B(sub o) as large as 2, fluxgate magnetometer measurements show relatively laminar shock transitions in three of the four events.

  3. The Supercritical Pile GRB Model: The Prompt to Afterglow Evolution

    Science.gov (United States)

    Mastichiadis, A.; Kazanas, D.

    2009-01-01

    The "Supercritical Pile" is a very economical GRB model that provides for the efficient conversion of the energy stored in the protons of a Relativistic Blast Wave (RBW) into radiation and at the same time produces - in the prompt GRB phase, even in the absence of any particle acceleration - a spectral peak at energy approx. 1 MeV. We extend this model to include the evolution of the RBW Lorentz factor Gamma and thus follow its spectral and temporal features into the early GRB afterglow stage. One of the novel features of the present treatment is the inclusion of the feedback of the GRB produced radiation on the evolution of Gamma with radius. This feedback and the presence of kinematic and dynamic thresholds in the model can be the sources of rich time evolution which we have began to explore. In particular. one can this may obtain afterglow light curves with steep decays followed by the more conventional flatter afterglow slopes, while at the same time preserving the desirable features of the model, i.e. the well defined relativistic electron source and radiative processes that produce the proper peak in the (nu)F(sub nu), spectra. In this note we present the results of a specific set of parameters of this model with emphasis on the multiwavelength prompt emission and transition to the early afterglow.

  4. Magnetohydrodynamically stable plasma with supercritical current density at the axis

    Energy Technology Data Exchange (ETDEWEB)

    Burdakov, A. V. [Budker Institute of Nuclear Physics, 11 Lavrentjev Avenue, 630090 Novosibirsk (Russian Federation); Novosibirsk State Technical University, 20 Karl Marks Avenue, 630092 Novosibirsk (Russian Federation); Postupaev, V. V., E-mail: V.V.Postupaev@inp.nsk.su; Sudnikov, A. V. [Budker Institute of Nuclear Physics, 11 Lavrentjev Avenue, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, 2 Pirogova st., 630090 Novosibirsk (Russian Federation)

    2014-05-15

    In this work, an analysis of magnetic perturbations in the GOL-3 experiment is given. In GOL-3, plasma is collectively heated in a multiple-mirror trap by a high-power electron beam. During the beam injection, the beam-plasma interaction maintains a high-level microturbulence. This provides an unusual radial profile of the net current (that consists of the beam current, current of the preliminary discharge, and the return current). The plasma core carries supercritical current density with the safety factor well below unity, but as a whole, the plasma is stable with q(a) ≈ 4. The net plasma current is counter-directed to the beam current; helicities of the magnetic field in the core and at the edge are of different signs. This forms a system with a strong magnetic shear that stabilizes the plasma core in good confinement regimes. We have found that the most pronounced magnetic perturbation is the well-known n = 1, m = 1 mode for both stable and disruptive regimes.

  5. Mechanistic and kinetic investigations on the role of methanol and dimethyl ether in the Methanol-To-Hydrocarbons reaction

    OpenAIRE

    Espín, Juan Salvador Martínez

    2017-01-01

    The main scope of this PhD thesis was to gain knowledge on the mechanistic and kinetic behavior of methanol and DME in the industrially relevant Methanol-To-Hydrocarbons (MTH) reaction with the use of zeolitic materials as catalysts. Industrial MTH processes use methanol, DME or combined methanol/DME feeds over zeolitic catalysts. Methanol and its dehydration product, DME, are conventionally attributed an analogous behavior in MTH; however, a thorough investigation on the theme is still missi...

  6. A New Biochemical Way for Conversion of CO2 to Methanol via Dehydrogenases Encapsulated in SiO2 Matrix

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    CO2 is converted to methanol through an enzymatic approach using formate dehydro- genase (FateDH), formaldehyde dehydrogenase (FaldDH) and alcohol dehydrogenase (ADH) co- encapsulated in silica gel prepared by modified sol-gel process as catalysts, TEOS as precursor, NADH as an electron donor. The highest yield of methanol was up to 92.1% under 37℃, pH7.0 and 0.3Mpa.

  7. Methanol exchange between grassland and the atmosphere

    Directory of Open Access Journals (Sweden)

    A. Brunner

    2007-01-01

    Full Text Available Concentrations and fluxes of methanol were measured above two differently managed grassland fields (intensive and extensive in central Switzerland during summer 2004. The measurements were performed with a proton-transfer-reaction mass-spectrometer and fluxes were determined by the eddy covariance method. The observed methanol emission showed a distinct diurnal cycle and was strongly correlated with global radiation and water vapour flux. Mean and maximum daily emissions were found to depend on grassland species composition and, for the intensive field, also on the growing state. The extensive field with a more complex species composition had higher emissions than the graminoid-dominated intensive field, both on an area and on a biomass basis. A simple parameterisation depending on the water vapour flux and the leaf area index allowed a satisfying simulation of the temporal variation of methanol emissions over the growing phase. Accumulated carbon losses due to methanol emissions accounted for 0.024 and 0.048% of net primary productivity for the intensive and extensive field, respectively. The integral methanol emissions over the growing periods were more than one order of magnitude higher than the emissions related to cut and drying events.

  8. Thermodynamic properties of supercritical carbon dioxide: Widom and Frenkel lines

    Science.gov (United States)

    Fomin, Yu. D.; Ryzhov, V. N.; Tsiok, E. N.; Brazhkin, V. V.

    2015-02-01

    Supercritical fluids are widely used in a number of important technological applications, yet the theoretical progress in the field has been rather moderate. Fairly recently, a new understanding of the liquidlike and gaslike properties of supercritical fluids has come to the fore, particularly with the advent of the Widom and Frenkel lines that aim to demarcate different physical properties on the phase diagram. Here, we report the results of a computational study of supercritical carbon dioxide, one of the most important fluids in the chemical industry. We study the response functions of CO2 in the supercritical state and calculate the locations of their maxima (Widom lines). We also report the preliminary calculations of the Frenkel line, the line of crossover of microscopic dynamics of particles. Our insights are relevant to physical processes in the atmosphere of Venus and its evolution.

  9. Supercritical Fluid Extraction of Aflatoxin B 1 from Soil

    Science.gov (United States)

    This research describes the development of a Supercritical Fluid Extraction (SFE) method to recover aflatoxin B1 from fortified soil. The effects of temperature, pressure, modifier (identity and percentage), and extraction type were assessed. Using the optimized SFE conditions, ...

  10. Measurement of Orotic Acid in Urine by Supercritical Fluid Chromatography

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    This work presents a simple, rapid and reliable supercritical fluid chromatography (SFC) method for a sensitive measurement of orotic acid in human urine. The samples were diluted with deionized water and analyzed directly without any pretreatment.

  11. Finite connections for supercritical Bernoulli bond percolation in 2D

    CERN Document Server

    Campanino, Massimo; Louidor, Oren

    2009-01-01

    Two vertices are said to be finitely connected if they belong to the same cluster and this cluster is finite. We derive sharp asymptotics for finite connection probabilities for supercritical Bernoulli bond percolation on Z^2.

  12. Supercritical fluid technology for energy and environmental applications

    CERN Document Server

    Anikeev, Vladimir

    2014-01-01

    Supercritical Fluid Technology for Energy and Environmental Applications covers the fundamental principles involved in the preparation and characterization of supercritical fluids (SCFs) used in the energy production and other environmental applications. Energy production from diversified resources - including renewable materials - using clean processes can be accomplished using technologies like SCFs. This book is focused on critical issues scientists and engineers face in applying SCFs to energy production and environmental protection, the innovative solutions they have found, and the challenges they need to overcome. The book also covers the basics of sub- and supercritical fluids, like the thermodynamics of phase and chemical equilibria, mathematical modeling, and process calculations. A supercritical fluid is any substance at a temperature and pressure above its critical point where distinct liquid and gas phases do not exist. At this state the compound demonstrates unique properties, which can be "fine...

  13. Supercritical Fluid Extraction of Aflatoxin B 1 from Soil

    Science.gov (United States)

    This research describes the development of a Supercritical Fluid Extraction (SFE) method to recover aflatoxin B1 from fortified soil. The effects of temperature, pressure, modifier (identity and percentage), and extraction type were assessed. Using the optimized SFE conditions, ...

  14. Physical properties of the benchmark models program supercritical wing

    Science.gov (United States)

    Dansberry, Bryan E.; Durham, Michael H.; Bennett, Robert M.; Turnock, David L.; Silva, Walter A.; Rivera, Jose A., Jr.

    1993-01-01

    The goal of the Benchmark Models Program is to provide data useful in the development and evaluation of aeroelastic computational fluid dynamics (CFD) codes. To that end, a series of three similar wing models are being flutter tested in the Langley Transonic Dynamics Tunnel. These models are designed to simultaneously acquire model response data and unsteady surface pressure data during wing flutter conditions. The supercritical wing is the second model of this series. It is a rigid semispan model with a rectangular planform and a NASA SC(2)-0414 supercritical airfoil shape. The supercritical wing model was flutter tested on a flexible mount, called the Pitch and Plunge Apparatus, that provides a well-defined, two-degree-of-freedom dynamic system. The supercritical wing model and associated flutter test apparatus is described and experimentally determined wind-off structural dynamic characteristics of the combined rigid model and flexible mount system are included.

  15. Plasticisation and complexation of certain polymers in supercritical CO2

    CSIR Research Space (South Africa)

    Labuschagne, Philip W

    2004-09-01

    Full Text Available A polymer system (polyvinylpyrrolidone + polyvinyl acetate-co-crotonic acid) was successfully identified for use as encapsulation material for sensitive actives using supercritical CO2 as plasticisation medium, having the following properties: 1...

  16. Extraction of lignite coal fly ash for polynuclear aromatic hydrocarbons: modified and unmodified supercritical fluid extraction, enhanced-fluidity solvents, and accelerated solvent extraction.

    Science.gov (United States)

    Kenny, D V; Olesik, S V

    1998-02-01

    A comparison among modified and unmodified supercritical fluid extraction (SFE), enhanced-fluidity liquid extraction, and accelerated solvent extraction (ASE) techniques was made for the extraction of polynuclear aromatic hydrocarbons (PAHs) from an aged, spiked lignite coal fly ash. All of the attempted extraction conditions allowed the extraction of the PAHs to some degree, but no single extraction technique proved to be superior for all of the PAHs used. Three groups of PAHs with similar extraction efficiencies were identified. The group with the lowest molecular weights was best recovered using a 90% CO2-10% methanol mixture at 70 degrees C and 238 atm. The group of medium-molecular-weight PAHs was recovered equally well using any of three extraction conditions: SFE (100% CO2, 90 degrees C, and 238 atm), enhanced-fluidity liquid mixture (60% CO2-40% methanol, 70 degrees C, and 238 atm), and a methanol ASE mixture. The group of high-molecular-weight PAHs seemed to be equally well recovered with all of the attempted extraction conditions, but the enhanced-fluidity conditions (60% CO2-40% methanol, 70 degrees C, and 238 atm) had extraction recoveries (> 85%) with the lowest standard deviations (approximately 5%).

  17. Supercritical fluid carbon dioxide extraction and liquid chromatographic separation with electrochemical detection of methylmercury from biological samples

    Science.gov (United States)

    Simon, N.S.

    1997-01-01

    Using the coupled methods presented in this paper, methylmercury can be accurately and rapidly extracted from biological samples by modified supercritical fluid carbon dioxide and quantitated using liquid chromatography with reductive electrochemical detection. Supercritical fluid carbon dioxide modified with methanol effectively extracts underivatized methylmercury from certified reference materials Dorm-1 (dogfish muscle) and Dolt-2 (dogfish liver). Calcium chloride and water, with a ratio of 5:2 (by weight), provide the acid environment required for extracting methylmercury from sample matrices. Methylmercury chloride is separated from other organomercury chloride compounds using HPLC. The acidic eluent, containing 0.06 mol L-1 NaCl, insures the presence of methylmercury chloride and facilitates the reduction of mercury on a glassy carbon electrode. If dual glassy carbon electrodes are used, a positive peak is observed at -0.65 to -0.70 V and a negative peak is observed at -0.90V with the organomercury compounds that were tested. The practical detection limit for methylmercury is 5 X 10-8 mol L-1 (1 X 10-12 tool injected) when a 20 ??L injection loop is used.

  18. Application of response surface methodology for the optimization of supercritical fluid extraction of essential oil from pomegranate (Punica granatum L.) peel.

    Science.gov (United States)

    Ara, Katayoun Mahdavi; Raofie, Farhad

    2016-07-01

    Essential oils and volatile components of pomegranate (Punica granatum L.) peel of the Malas variety from Meybod, Iran, were extracted using supercritical fluid extraction (SFE) and hydro-distillation methods. The experimental parameters of SFE that is pressure, temperature, extraction time, and modifier (methanol) volume were optimized using a central composite design after a (2(4-1)) fractional factorial design. Detailed chemical composition of the essential oils and volatile components obtained by hydro-distillation and optimum condition of the supercritical CO2 extraction were analyzed by GC-MS, and seventy-three and forty-six compounds were identified according to their retention indices and mass spectra, respectively. The optimum SFE conditions were 350 atm pressure, 55 °C temperature, 30 min extraction time, and 150 µL methanol. Results showed that oleic acid, palmitic acid and (-)-Borneol were major compounds in both extracts. The optimum extraction yield was 1.18 % (w/w) for SFE and 0.21 % (v/w) for hydro-distillation.

  19. Determination of solvation kinetics in supercritical fluids. Summary report

    Energy Technology Data Exchange (ETDEWEB)

    Bright, F.V.

    1993-01-01

    Objective was to study solvation processes in pure and entrainer-modified supercritical fluids. Specific topics were: Kinetics for solvation in supercritical media, influence on entrainers on solvation, reversibility of solvation, effects of solvation on intramolecular solute-solute interaction kinetics, and impact of fluid density on these processes. Time-resolved fluorescence spectroscopy was used as the main analytical tool. A summary is given of the 2.5 years` research.

  20. Supercritical hydrogenation and acid-catalysed reactions "without gases".

    Science.gov (United States)

    Hyde, Jason R; Poliakoff, Martyn

    2004-07-07

    The high temperature catalytic decomposition of HCO2H and HCO2Et are used to generate the high pressure H2 and the supercritical fluids needed for micro-scale hydrogenation of organic compounds; our approach overcomes the problems and limitations of handling high pressure gases on a small-scale and opens the way to the widespread use of continuous supercritical reactions in the laboratory.

  1. Research in Supercritical Fuel Properties and Combustion Modeling

    Science.gov (United States)

    2015-09-18

    any significant impact on the normal hydrocarbon oxidation kinetics . These are ethanol, dimethyl ether( DME ), and methyl formate (C2H5OH, CH3OCH3...research are to develop stimulated scattering as a diagnostic for supercritical fluids, and to evaluate reaction kinetics inputs involving 2-4...measurements for refractive index measurements, and tested our supercritical cell. On the reaction kinetics task, review and evaluation of reactions, rate

  2. Fischer-Tropsch synthesis in supercritical fluids. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Akgerman, A.; Bukur, D.B.

    1998-12-31

    The objective of this study was to investigate Fischer-Tropsch Synthesis (FTS) in the supercritical phase employing a commercial precipitated iron catalysts. As the supercritical fluid the authors used propane and n-hexane. The catalyst had a nominal composition of 100 Fe/5 Cu/4.2 K/25 SiO{sub 2} on mass basis and was used in a fixed bed reactor under both normal (conventional) and supercritical conditions. Experimental data were obtained at different temperatures (235 C, 250 C, and 260 C) and synthesis gas feed compositions (H{sub 2}/CO molar feed ratio of 0.67, 1.0 and 2.0) in both modes of operation under steady state conditions. The authors compared the performance of the precipitated iron catalyst in the supercritical phase, with the data obtained in gas phase (fixed bed reactor) and slurry phase (STS reactor). Comparisons were made in terms of bulk catalyst activity and various aspects of product selectivity (e.g. lumped hydrocarbon distribution and olefin content as a function of carbon number). In order to gain better understanding of the role of intraparticle mass transfer during FTS under conventional or supercritical conditions, the authors have measured diffusivities of representative hydrocarbon products in supercritical fluids, as well as their effective diffusion rates into the pores of catalyst at the reaction conditions. They constructed a Taylor dispersion apparatus to measure diffusion coefficients of hydrocarbon products of FTS in sub and supercritical ethane, propane, and hexane. In addition, they developed a tracer response technique to measure the effective diffusivities in the catalyst pores at the same conditions. Based on these results they have developed an equation for prediction of diffusion in supercritical fluids, which is based on the rough hard sphere theory.

  3. Electrochemistry in Near-Critical and Supercritical Fluids. I. Ammonia.

    Science.gov (United States)

    1984-07-18

    in a supercritical fluid containing an electrolyte. We show j here that electrocheical techniques, such as cyclic voltametry and .’ chronocoulametrY...8217,_- Electrochemistry, supercritical, ammonia S&. ASSTRACT. (CGWIU&UI VOWO *fo of Rea@ d 8~ US F &I-*I 81116 Cyclic voltanmetric and chronocoulometric studies of N...Bard 4 Department of Chemi stry, The University of Texas Austin, TX 78712 (Abstract) Cyclic voittuuntric and chronocoulometric studies of NH3

  4. Independent Research and Design of 600-MW Supercritical CFB Boiler

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    In order to further develop and improve the technologies for large-capacity supercritical CFB boiler, the key technologies for large CFB boiler were systematically studied, based on the development of first domestically-made 210-MW and 330-MW CFB boilers. The scheme of 600-MW supercritical CFB boiler was designed, including the furnace structure, key components, steam-water system and auxiliary systems, which laid a technical foundation for the engineering applications.

  5. Isolation of Organochlorine Pesticide from Ginseng with Supercritical CO2

    Institute of Scientific and Technical Information of China (English)

    李淑芬; 王幼君; 全灿; 田松江

    2005-01-01

    The feasibility of removal of the organochlorine pesticides residues of hexachlorocyclohexane(BHC) from radix ginseng with supercritical CO2 was explored. Some factors, such as extraction pressure, extraction temperature, and kinds of co-solvents were investigated. The experimental results indicate that it is possible to reduce BHC residues in radix ginseng to the level of 0.1 × 10-6 with supercritical CO2 in the presence of suitable amount of co-solvent, such as water.

  6. Extraction of olive oil with supercritical carbon dioxide / Ilana Geerdts

    OpenAIRE

    Geerdts, Ilana

    2005-01-01

    The principal objective of this study was to extract olive oil from the fruit of Olea europaea by means of supercritical carbon dioxide (sc-C02) as an alternative to traditional methods. Extractions were performed on a laboratory scale supercritical fluid extractor of the latest design, featuring three mutually independent flow systems and extremely high flow rates. A number of extraction runs based on a statistical design was performed to establish the conditions (time, pressu...

  7. Radiolysis study of genistein in methanolic solution

    Science.gov (United States)

    Jung, Hee Jin; Park, Hae Ran; Jung, Uhee; Jo, Sung Kee

    2009-06-01

    The aim of the present work was to identify products obtained from genistein by ionizing radiation and to enhance the antioxidant properties of genistein through radiation-induced transformation. Genistein dissolved in methanol was irradiated γ-rays at a dose of 100 kGy. NMR and (HR) EI-MS spectroscopy were used to identify radiolysis products (GM1 and GM2). We proposed that rad CH 2OH may be implicated in the formation GM1 and GM2 during radiolysis of genistein in methanol. The genistein in methanol solution showed higher DPPH radical scavenging activity after γ-irradiation. Then, the antioxidant activities of radiolysis products were evaluated and compared to those of genistein.

  8. Methanol sensor operated in a passive mode

    Science.gov (United States)

    Ren, Xiaoming; Gottesfeld, Shimshon

    2002-01-01

    A sensor outputs a signal related to a concentration of methanol in an aqueous solution adjacent the sensor. A membrane electrode assembly (MEA) is included with an anode side and a cathode side. An anode current collector supports the anode side of the MEA and has a flow channel therethrough for flowing a stream of the aqueous solution and forms a physical barrier to control access of the methanol to the anode side of the MEA. A cathode current collector supports the cathode side of the MEA and is configured for air access to the cathode side of the MEA. A current sensor is connected to measure the current in a short circuit across the sensor electrodes to provide an output signal functionally related to the concentration of methanol in the aqueous solution.

  9. Polarisation of Class II Methanol Masers

    CERN Document Server

    Stack, P D

    2011-01-01

    We have used the University of Tasmania Mt Pleasant 26m radio telescope to investigate the polarisation characteristics of a sample of strong 6.7 GHz methanol masers, the first spectral line polarisation observations to be undertaken with this instrument. As part of this process we have developed a new technique for calibrating linear polarisation spectral line observations. This calibration method gives results consistent with more traditional techniques, but requires much less observing time on the telescope. We have made the first polarisation measurements of a number of 6.7 GHz methanol masers and find linear polarisation at levels of a few - 10% in most of the sources we observed, consistent with previous results. We also investigated the circular polarisation produced by Zeeman splitting in the 6.7 GHz methanol maser G9.62+0.20 to get an estimate of the line of sight magnetic field strength of 35+/-7 mG.

  10. Efficient green methanol synthesis from glycerol

    Science.gov (United States)

    Haider, Muhammad H.; Dummer, Nicholas F.; Knight, David W.; Jenkins, Robert L.; Howard, Mark; Moulijn, Jacob; Taylor, Stuart H.; Hutchings, Graham J.

    2015-12-01

    The production of biodiesel from the transesterification of plant-derived triglycerides with methanol has been commercialized extensively. Impure glycerol is obtained as a by-product at roughly one-tenth the mass of the biodiesel. Utilization of this crude glycerol is important in improving the viability of the overall process. Here we show that crude glycerol can be reacted with water over very simple basic or redox oxide catalysts to produce methanol in high yields, together with other useful chemicals, in a one-step low-pressure process. Our discovery opens up the possibility of recycling the crude glycerol produced during biodiesel manufacture. Furthermore, we show that molecules containing at least two hydroxyl groups can be converted into methanol, which demonstrates some aspects of the generality of this new chemistry.

  11. Effects of methanol on the growth of gastrointestinal anaerobes

    Energy Technology Data Exchange (ETDEWEB)

    Caldwell, D.R. (Univ. of Wyoming, Laramie, WY (USA))

    1989-01-01

    The effects of methanol on the growth of representative, predominant, anaerobic gut bacteria were studied. Growth yields and rates were determined in a base medium to which methanol was added to produce media with methanol concentrations varying, in twofold steps, over a concentration range of 0.01 to 25%, by volume. The growth of many of the organisms were completely inhibited by a methanol concentration equal to, or less than, 6.2%. Isolates representing cellulolytic species were completely inhibited at a methanol concentration of 3.1%, and inhibitory effects on the yield of some cellulolytic isolates were found at a methanol concentration as small as 0.01%. Although most of the organisms studied were inhibited at relatively small methanol concentrations, isolates of Selenomonas ruminantium, Bacteroides ovatus, and Fusobacterium necrophorum were relatively methanol resistant. A methanol concentration of 12.5% was required to completely inhibit S. ruminantium. Substantial growth of B. ovatus was obtained in media containing 12.5% methanol, and for F. necrophorum, substantial growth occurred in media containing 25% methanol. The yields of F. necrophorum strain B85 and S. ruminantum strain PC18 were enhanced by relatively small methanol concentrations and reduced with further methanol concentration increase. Anaerobic, nonsporing gut bacteria exhibit a diversity of responses to methanol. 12 refs., 2 figs., 4 tabs.

  12. Hydrogenation of diesel aromatic compounds in supercritical solvent environment

    Directory of Open Access Journals (Sweden)

    E.P. Martins

    2000-09-01

    Full Text Available Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface, or even some gas-phase reactions. Basically, a supercritical solvent can diminish the reactant’s transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, i.e., to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed.

  13. Effects of Gravity on Supercritical Water Oxidation (SCWO) Processes

    Science.gov (United States)

    Hegde, Uday; Hicks, Michael

    2013-01-01

    The effects of gravity on the fluid mechanics of supercritical water jets are being studied at NASA to develop a better understanding of flow behaviors for purposes of advancing supercritical water oxidation (SCWO) technologies for applications in reduced gravity environments. These studies provide guidance for the development of future SCWO experiments in new experimental platforms that will extend the current operational range of the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on board the International Space Station (ISS). The hydrodynamics of supercritical fluid jets is one of the basic unit processes of a SCWO reactor. These hydrodynamics are often complicated by significant changes in the thermo-physical properties that govern flow behavior (e.g., viscosity, thermal conductivity, specific heat, compressibility, etc), particularly when fluids transition from sub-critical to supercritical conditions. Experiments were conducted in a 150 ml reactor cell under constant pressure with water injections at various flow rates. Flow configurations included supercritical jets injected into either sub-critical or supercritical water. Profound gravitational influences were observed, particularly in the transition to turbulence, for the flow conditions under study. These results will be presented and the parameters of the flow that control jet behavior will be examined and discussed.

  14. Hydrogenation of diesel aromatic compounds in supercritical solvent environment

    Energy Technology Data Exchange (ETDEWEB)

    Martins, E.P.; Aranda, D.A.G.; Pessoa, F.L.P. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Escola de Quimica. Dept. de Engenharia Quimica. E-mail: donato@h2o.eq.ufrj.br; pessoa@h2o.eq.ufrj.br; Zotin, J.L. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas. E-mail: zotin@cenpes.petrobras.com.br

    2000-09-01

    Reactions under supercritical conditions have been employed in many processes. Furthermore, an increasing number of commercial reactions have been conducted under supercritical or near critical conditions. These reaction conditions offer several advantages when compared to conditions in conventional catalytic processes in liquid-phase, gas-liquid interface., or even some gas-phase reactions. basically, a supercritical solvent can diminish the reactant's transport resistance from the bulk region to the catalyst surface due to enhancement of liquid diffusivity values and better solubility than those in different phases. Another advantage is that supercritical solvents permit prompt and easy changes in intermolecular properties in order to modify reaction parameters, such as conversion or selectivity, or even proceed with the separation of reaction products. Diesel fractions from petroleum frequently have larger than desirable quantities of aromatic compounds. Diesel hydrogenation is intended to decrease these quantities, to increase the quantity of paraffin present in this petroleum fraction. In this work, the hydrogenation of tetralin was studied as a model reaction for the aromatic hydrogenation process. A conventional gas-liquid-solid catalytic process was compared with that of supercritical carbon dioxide substrate under similar conditions. Additionally, an equilibrium conversion diagram was calculated for this reaction in a wide range of temperature and reactant ratios, so as to optimize the operational conditions and improve the results of subsequent experiments. An increase in the rate of reaction at 493 K in supercritical fluid, as compared to that in the conventional process, was observed. (author)

  15. Supercritical extraction of lycopene from tomato industrial wastes with ethane.

    Science.gov (United States)

    Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

    2012-07-11

    Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

  16. Ni/Pd-Decorated Carbon NFs as an Efficient Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Science.gov (United States)

    Mohamed, Ibrahim M. A.; Khalil, Khalil Abdelrazek; Mousa, Hamouda M.; Barakat, Nasser A. M.

    2017-01-01

    In this study, Ni/Pd-decorated carbon nanofibers (NFs) were fabricated as an electrocatalyst for methanol oxidation. These NFs were synthesized based on carbonization of poly(vinyl alcohol), which has high carbon content compared to many polymers used to prepare carbon NFs. Typically, calcination of an electrospun mat composed of nickel acetate, palladium acetate, and poly(vinyl alcohol) can produce Ni/Pd-doped carbon NFs. The introduced NFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy, line TEM energy dispersive x-ray spectrometry, field emission scanning electron microscopy, and x-ray powder diffraction. These physicochemical characterizations are acceptable tools to investigate the crystallinity and chemistry of the fabricated Ni/Pd-carbon NFs. Accordingly, the prepared NFs were tested to enhance the economic and catalytic behavior of methanol electrooxidation. Experimentally, the obtained onset potential was small compared to many reported materials; 0.32 V (versus Ag/AgCl as a reference electrode). At the same time, the current density changed from 5.08 mA/cm2 in free methanol at 0.6 V to 12.68 mA/cm2 in 0.1 mol/L methanol, which can be attributed to the MeOH oxidation. Compared to nanoparticles, the NFs have a distinct effect on the electrocatalytic performance of material due to the effect of the one-dimensional structure, which facilitates the electron transfer. Overall, the presented work opens a new way for non-precious one-dimensional nanostructured catalysts for direct methanol fuel cell technology.

  17. Ni/Pd-Decorated Carbon NFs as an Efficient Electrocatalyst for Methanol Oxidation in Alkaline Medium

    Science.gov (United States)

    Mohamed, Ibrahim M. A.; Khalil, Khalil Abdelrazek; Mousa, Hamouda M.; Barakat, Nasser A. M.

    2016-09-01

    In this study, Ni/Pd-decorated carbon nanofibers (NFs) were fabricated as an electrocatalyst for methanol oxidation. These NFs were synthesized based on carbonization of poly(vinyl alcohol), which has high carbon content compared to many polymers used to prepare carbon NFs. Typically, calcination of an electrospun mat composed of nickel acetate, palladium acetate, and poly(vinyl alcohol) can produce Ni/Pd-doped carbon NFs. The introduced NFs were characterized by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy, line TEM energy dispersive x-ray spectrometry, field emission scanning electron microscopy, and x-ray powder diffraction. These physicochemical characterizations are acceptable tools to investigate the crystallinity and chemistry of the fabricated Ni/Pd-carbon NFs. Accordingly, the prepared NFs were tested to enhance the economic and catalytic behavior of methanol electrooxidation. Experimentally, the obtained onset potential was small compared to many reported materials; 0.32 V (versus Ag/AgCl as a reference electrode). At the same time, the current density changed from 5.08 mA/cm2 in free methanol at 0.6 V to 12.68 mA/cm2 in 0.1 mol/L methanol, which can be attributed to the MeOH oxidation. Compared to nanoparticles, the NFs have a distinct effect on the electrocatalytic performance of material due to the effect of the one-dimensional structure, which facilitates the electron transfer. Overall, the presented work opens a new way for non-precious one-dimensional nanostructured catalysts for direct methanol fuel cell technology.

  18. Kinetics of methanol electrooxidation on Pt/C and PtRu/C catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, V.; Ohanian, M. [Instituto de Ingenieria Quimica, Facultad de Ingenieria, J. Herrera y Reissig 565, Universidad de la Republica, 11300 Montevideo (Uruguay); Zinola, C.F. [Laboratorio de Electroquimica Fundamental, Facultad de Ciencias, Igua 4225, Universidad de la Republica, 11400 Montevideo (Uruguay)

    2010-10-15

    This paper analyzes the performance of platinum and platinum:ruthenium carbon-supported catalysts modified by the application of in-situ cathodic polarizations towards the methanol oxidation reaction. These new electrodes are characterized by electrochemical techniques together with transmission electron microscopy images to envisage the dispersion of the catalyst. We measure methanol electrooxidation current transients, fitting the results with a general kinetic equation for a mixed mass and charge transfer processes for adsorbed reactant species. The kinetic equation also helps to predict the exponent of the chronoamperometric decay as directly related to the fractal dimension of the catalyst surface and to discuss the possible processes involved in the electrocatalytic reaction. (author)

  19. Quantifying the promotion of Cu catalysts by ZnO for methanol synthesis

    DEFF Research Database (Denmark)

    Kuld, Sebastian; Thorhauge, Max; Falsig, Hanne

    2016-01-01

    Promoter elements enhance the activity and selectivity of heterogeneous catalysts. Here, we show how methanol synthesis from synthesis gas over copper (Cu) nanoparticles is boosted by zinc oxide (ZnO) nanoparticles. By combining surface area titration, electron microscopy, activity measurement......, density functional theory calculations, and modeling, we show that the promotion is related to Zn atoms migrating in the Cu surface. The Zn coverage is quantitatively described as a function of the methanol synthesis conditions and of the size-dependent thermodynamic activities of the Cu and Zn...

  20. Low-Pt-Content Anode Catalyst for Direct Methanol Fuel Cells

    Science.gov (United States)

    Narayanan, Sekharipuram; Whitacre, Jay

    2008-01-01

    Combinatorial experiments have led to the discovery that a nanophase alloy of Pt, Ru, Ni, and Zr is effective as an anode catalyst material for direct methanol fuel cells. This discovery has practical significance in that the electronic current densities achievable by use of this alloy are comparable or larger than those obtained by use of prior Pt/Ru catalyst alloys containing greater amounts of Pt. Heretofore, the high cost of Pt has impeded the commercialization of direct methanol fuel cells. By making it possible to obtain a given level of performance at reduced Pt content (and, hence, lower cost), the discovery may lead to reduction of the economic impediment to commercialization.

  1. Photocatalytic conversion of methane to methanol

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, C.E.; Noceti, R.P.; D`Este, J.R. [Pittsburgh Energy Technology Center, PA (United States)

    1995-12-31

    A long-term goal of our research group is the exploration of novel pathways for the direct oxidation of methane to liquid fuels, chemicals, and intermediates. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol is attractive. The products of reaction, methanol and hydrogen, are both commercially desirable, methanol being used as is or converted to a variety of other chemicals, and the hydrogen could be utilized in petroleum and/or chemical manufacturing. Methane is produced as a by-product of coal gasification. Depending upon reactor design and operating conditions, up to 18% of total gasifier product may be methane. In addition, there are vast proven reserves of geologic methane in the world. Unfortunately, a large fraction of these reserves are in regions where there is little local demand for methane and it is not economically feasible to transport it to a market. There is a global research effort under way in academia, industry, and government to find methods to convert methane to useful, more readily transportable and storable materials. Methanol, the initial product of methane oxidation, is a desirable product of conversion because it retains much of the original energy of the methane while satisfying transportation and storage requirements. Investigation of direct conversion of methane to transportation fuels has been an ongoing effort at PETC for over 10 years. One of the current areas of research is the conversion of methane to methanol, under mild conditions, using light, water, and a semiconductor photocatalyst. The use of three relatively abundant and inexpensive reactants, light, water, and methane, to produce methanol, is attractive. Research in the laboratory is directed toward applying the techniques developed for the photocatalytic splitting of the water and the photochemical conversion of methane.

  2. High Materials Performance in Supercritical CO2 in Comparison with Atmospheric Pressure CO2 and Supercritical Steam

    Energy Technology Data Exchange (ETDEWEB)

    Holcomb, Gordon [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Tylczak, Joseph [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Carney, Casey [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Dogan, Omer N. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

    2017-02-26

    This presentation covers environments (including advanced ultra-supercritical (A-USC) steam boiler/turbine and sCO2 indirect power cycle), effects of pressure, exposure tests, oxidation results, and mechanical behavior after exposure.

  3. Formation of energetic materials using supercritical fluids

    Energy Technology Data Exchange (ETDEWEB)

    Teipel, U.; Kroeber, H.; Krause, H.H. [Fraunhofer-Institut fuer Chemische Technologie (ICT), Pfinztal (Germany)

    2001-10-01

    A new field of applications of compressed gases is the formation of solid particles with well-defined properties, e.g. the particle size, the particle size distribution, the particle shape, the specific surface area and free of solvent inclusions. It is possible to process moderately solids like energetic materials which are difficult to comminute due to their sensitivity to mechanical or thermal stress. The characteristics of compressed gases allow to vary the morphology of solid particles in a wide range. A pilot plant is presented, which has been built to prepare fine particles by the rapid expansion of supercritical solutions (RESS process) and precipitation by a compressed fluid antisolvent (PCA process). In this contribution the micronization of different energetic materials by the RESS and PCA processes will be under investigation. (orig.)

  4. Thermodynamic properties of superheated and supercritical steam

    Energy Technology Data Exchange (ETDEWEB)

    Malhotra, A. [Indian Inst. of Technology, New Delhi (India). Dept. of Mechanical Engineering; Panda, D.M.R. [Dadri Gas Power Station, NTPC, Gautam Buddha Nagar (India)

    2001-07-01

    An existing formulation for steam properties is due to Irvine and Liley. Their equations are convenient to program and do not require excessive computational time to produce results. The properties computed from these equations compare favourably with standard data. An additional advantage of these equations is that they follow prescribed theoretical trends by reducing to perfect-gas behaviour away from the saturation dome. However, a difficulty with these equations is that, at pressures above 10 MPa and close to the saturation dome, unacceptably large errors (above 10%) are produced. These equations are examined in the present work with a view towards enhancing their range of application through the use of additional functions. It is shown that the errors may be reduced to within 1% over the entire range of pressures (both sub-critical and super-critical pressures) required in steam-plant calculations. (author)

  5. Gasification of cyanobacterial in supercritical water.

    Science.gov (United States)

    Zhang, Huiwen; Zhu, Wei; Xu, Zhirong; Gong, Miao

    2014-01-01

    Cyanobacterial collected from eutrophic freshwater lakes constituted intractable waste with a rich algae biomass content. Supercritical water gasification (SCWG) was proposed to treat the cyanobacterial and to produce hydrogen for energy. The H 2 yield reached 2.92 mol/kg at reaction conditions of 500 °C, 30 min and 22 MPa; this yield accounted for 26% of the total gaseous products. Abundant ammonia and dissolved reactive phosphorous were concentrated in the liquid product, which could be recovered and used as a liquid fertilizer. Solid residue, which accounted only for about 1% of the wet weight, was mainly composed of coke and ash. The efficiency of H 2 production was better than that from other biomass, because of the abundant organic matter in cyanobacterial. Thus, cyanobacterial are an ideal biomass feedstock for H 2 production from SCWG.

  6. Supercritical droplet combustion and related transport phenomena

    Science.gov (United States)

    Yang, Vigor; Hsieh, K. C.; Shuen, J. S.

    1993-01-01

    An overview of recent advances in theoretical analyses of supercritical droplet vaporization and combustion is conducted. Both hydrocarbon and cryogenic liquid droplets over a wide range of thermodynamic states are considered. Various important high-pressure effects on droplet behavior, such as thermodynamic non-ideality, transport anomaly, and property variation, are reviewed. Results indicate that the ambient gas pressure exerts significant control of droplet gasification and burning processes through its influence on fluid transport, gas-liquid interfacial thermodynamics, and chemical reactions. The droplet gasification rate increases progressively with pressure. However, the data for the overall burnout time exhibit a considerable change in the combustion mechanism at the criticl pressure, mainly as a result of reduced mass diffusivity and latent heat of vaporization with increased pressure. The influence of droplet size on the burning characteristics is also noted.

  7. Supercritical Antisolvent Precipitation of Microparticles of Quercetin

    Institute of Scientific and Technical Information of China (English)

    刘学武; 李志义; 韩冰; 苑塔亮

    2005-01-01

    Supercritical antisolvent (SAS) process is a recently developed technology to produce micro- and nanoparticles. This paper presents a continuous apparatus to conduct experiment of SAS process. With the apparatus,the effects of pressure, temperature and flow ratio of CO2 to the solution on the shape and size of particles are studied for the quercetin-ethanol-CO2 system. Spherical quercetin microparticles with diameters ranging form i μm to 6μm can be obtained while ethanol is used as organic solvent. The most effective fact on the shape and size of particles is pressure, the next is temperature and the last is the flow ratio of CO2 to solution.

  8. Large-Amplitude Electrostatic Waves Observed at a Supercritical Interplanetary Shock

    Science.gov (United States)

    Wilson, L. B., III; Cattell, C. A.; Kellogg, P. J.; Goetz, K.; Kersten, K.; Kasper, J. C.; Szabo, A.; Wilber, M.

    2010-01-01

    We present the first observations at an interplanetary shock of large-amplitude (> 100 mV/m pk-pk) solitary waves and large-amplitude (approx.30 mV/m pk-pk) waves exhibiting characteristics consistent with electron Bernstein waves. The Bernstein-like waves show enhanced power at integer and half-integer harmonics of the cyclotron frequency with a broadened power spectrum at higher frequencies, consistent with the electron cyclotron drift instability. The Bernstein-like waves are obliquely polarized with respect to the magnetic field but parallel to the shock normal direction. Strong particle heating is observed in both the electrons and ions. The observed heating and waveforms are likely due to instabilities driven by the free energy provided by reflected ions at this supercritical interplanetary shock. These results offer new insights into collisionless shock dissipation and wave-particle interactions in the solar wind.

  9. Abacavir methanol 2.5-solvate

    Directory of Open Access Journals (Sweden)

    Phuong-Truc T. Pham

    2009-08-01

    Full Text Available The structure of abacavir (systematic name: {(1S,4R-4-[2-amino-6-(cyclopropylamino-9H-purin-9-yl]cyclopent-2-en-1-yl}methanol, C14H18N6O·2.5CH3OH, consists of hydrogen-bonded ribbons which are further held together by additional hydrogen bonds involving the hydroxyl group and two N atoms on an adjacent purine. The asymmetric unit also contains 2.5 molecules of methanol solvate which were grossly disordered and were excluded using SQUEEZE subroutine in PLATON [Spek, (2009. Acta Cryst. D65, 148–155].

  10. Silicon Based Direct Methanol Fuel Cells

    DEFF Research Database (Denmark)

    Larsen, Jackie Vincent

    The purpose of this project has been to investigate and fabricate small scale Micro Direct Methanol Fuel Cells (μDMFC). They are investigated as a possible alternative for Zinc-air batteries in small size consumer devices such as hearing aids. In such devices the conventional rechargeable batteries...... such as lithium-ion batteries have insufficiently low energy density. Methanol is a promising fuel for such devices due to the high energy density and ease of refueling compared to charging batteries, making μDMFC a suitable replacement energy source. In this Ph.D. dissertation, silicon micro fabrication...

  11. Synthesis and Optimization of a Methanol Process

    DEFF Research Database (Denmark)

    Grue, J.; Bendtsen, Jan Dimon

    2003-01-01

    In the present paper, a simulation model for a methanol process is proposed. The objective is to develop a model for flowsheet optimization, which requires simple thermodynamic and unit operation models. Simplified thermodynamic models are combined with a more advanced model for the rate of react......In the present paper, a simulation model for a methanol process is proposed. The objective is to develop a model for flowsheet optimization, which requires simple thermodynamic and unit operation models. Simplified thermodynamic models are combined with a more advanced model for the rate...

  12. Supercritical water oxidation of landfill leachate.

    Science.gov (United States)

    Wang, Shuzhong; Guo, Yang; Chen, Chongming; Zhang, Jie; Gong, Yanmeng; Wang, Yuzhen

    2011-01-01

    In this paper, ammonia as an important ingredient in landfill leachate was mainly studied. Based on Peng-Robinson formulations and Gibbs free energy minimization method, the estimation of equilibrium composition and thermodynamic analysis for supercritical water oxidation of ammonia (SCWO) was made. As equilibrium is reached, ammonia could be totally oxidized in SCW. N(2) is the main product, and the formation of NO(2) and NO could be neglected. The investigation on SCWO of landfill leachate was conducted in a batch reactor at temperature of 380-500 °C, reaction time of 50-300s and pressure of 25 MPa. The effect of reaction parameters such as oxidant equivalent ratio, reaction time and temperature were investigated. The results showed that COD and NH(3) conversion improved as temperature, reaction time and oxygen excess increased. Compared to organics, NH(3) is a refractory compound in supercritical water. The conversion of COD and NH(3) were higher in the presence of MnO(2) than that without catalyst. The interaction between reaction temperature and time was analyzed by using response surface method (RSM) and the results showed that its influence on the NH(3) conversion was relatively insignificant in the case without catalyst. A global power-law rate expression was regressed from experimental data to estimate the reaction rate of NH(3). The activation energy with and without catalyst for NH(3) oxidation were 107.07 ± 8.57 kJ/mol and 83.22 ± 15.62 kJ/mol, respectively.

  13. 37 GHz methanol masers : Horsemen of the Apocalypse for the class II methanol maser phase?

    CERN Document Server

    Ellingsen, S P; Sobolev, A M; Voronkov, M A; Caswell, J L; Lo, N

    2011-01-01

    We report the results of a search for class II methanol masers at 37.7, 38.3 and 38.5 GHz towards a sample of 70 high-mass star formation regions. We primarily searched towards regions known to show emission either from the 107 GHz class II methanol maser transition, or from the 6.035 GHz excited OH transition. We detected maser emission from 13 sources in the 37.7 GHz transition, eight of these being new detections. We detected maser emission from three sources in the 38 GHz transitions, one of which is a new detection. We find that 37.7 GHz methanol masers are only associated with the most luminous 6.7 and 12.2 GHz methanol maser sources, which in turn are hypothesised to be the oldest class II methanol sources. We suggest that the 37.7 GHz methanol masers are associated with a brief evolutionary phase (of 1000-4000 years) prior to the cessation of class II methanol maser activity in the associated high-mass star formation region.

  14. METHANOL REMOVAL FROM METHANOL-WATER MIXTURE USING ACTIVATED SLUDGE, AIR STRIPPING AND ADSORPTION PROCESS: COMPARATIVE STUDY

    Directory of Open Access Journals (Sweden)

    SALAM K. AL-DAWERY

    2015-12-01

    Full Text Available An experimental research has been carried out in order to examine the removal of methanol from methanol-water mixtures using three different methods; activated sludge; activated carbon and air stripping. The results showed that the methanol was totally consumed by the bacteria as quickly as the feed entered the activated sludge vessel. Air stripping process has a limited ability for removing of methanol due to strong intermolecular forces between methanol and water; however, the results showed that the percentage of methanol removed using air pressure at 0.5 bar was higher than that of using air pressure of 0.25 bar. Removal of methanol from the mixture with a methanol content of 5% using activated carbon was not successful due to the limited capacity of the of the activated carbon. Thus, the activated sludge process can be considered as the most suitable process for the treatment of methanol-water mixtures.

  15. Sequential Electrodeposition of Platinum-Ruthenium at Boron-Doped Diamond Electrodes for Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Ileana González-González

    2011-01-01

    Full Text Available Sequential electrodeposition of Pt and Ru on boron-doped diamond (BDD films, in 0.5 M H2SO4 by cyclic voltammetry, has been prepared. The potential cycling, in the aqueous solutions of the respective metals, was between 0.00 and 1.00 V versus Ag/AgCl. The catalyst composites, Pt and PtRu, deposited on BDD film substrates, were tested for methanol oxidation. The modified diamond surfaces were also characterized by scanning electron microscopy-X-ray fluorescence-energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The scanning Auger electron spectroscopy mapping showed the ruthenium signal only in areas where platinum was electrodeposited. Ruthenium does not deposit on the oxidized diamond surface of the boron-doped diamond. Particles with 5–10% of ruthenium with respect to platinum exhibited better performance for methanol oxidation in terms of methanol oxidation peak current and chronoamperometric current stability. The electrogenerated •OH radicals on BDD may interact with Pt surface, participating in the methanol oxidation as shown in oxidation current and the shift in the peak position. The conductive diamond surface is a good candidate as the support for the platinum electrocatalyst, because it ensures catalytic activity, which compares with the used carbon, and higher stability under severe anodic and cathodic conditions.

  16. Effect of Methanol Crossover in a Liquid-FeedPolymer-Electrolyte Direct Methanol Fuel Cell

    OpenAIRE

    Ravikumar, MK; Shukla, AK

    1996-01-01

    The performance of a liquid-feed direct methanol fuel cell employing a proton-exchange membrane electrolyte with Pt-Ru/C as anode and Pt/C as cathode is reported. The fuel cell can deliver a power density of ca. 0.2 $W/cm^2$ at 95°C, sufficient to suggest that the stack construction is well worthwhile.Methanol crossover across the polymer electrolyte at concentrations beyond 2 M methanol affects the performance of the cell which appreciates with increasing operating temperature.

  17. Effect of Lanthanum on Methanol Fuel Exhaust Deep Oxidation over Pall adium Catalyst

    Institute of Scientific and Technical Information of China (English)

    王幸宜; 万颖; 卢冠忠

    2003-01-01

    The performance of deep oxidation of methanol on supported Pd catalyst was examined by a chromatograph-micro-reactor. The results show that the addition of La into γ-Al2O3 support can affect greatly the performance of the Pd catalyst. In the absence of CO, La can decrease the content of oxygen-containing intermediate, although La can not lower the light-off temperature of methanol oxidation. In the presence of CO, La can lower the light-off temperature, decrease the amount of CO adsorption, and weaken evidently "CO inhibition" to the oxidation of methanol. By XPS technique, it is shown that La modifies the electronic structure of Pd, which attributes to the modifications of the catalytic performance.

  18. Development of multi-layered microreactor with methanol reformer for small PEMFC

    Energy Technology Data Exchange (ETDEWEB)

    Terazaki, Tsutomu; Nomura, Masatoshi; Takeyama, Keishi; Nakamura, Osamu; Yamamoto, Tadao [CASIO Computer CO., Ltd., 10-6 Imai 3-chome, Oume-shi, Tokyo 198-8555 (Japan)

    2005-08-18

    A glass multi-layered microreactor with a methanol reformer that could provide power to portable electronic devices was developed to supply hydrogen to a small proton exchange membrane fuel cell (PEMFC). The microreactor consisted of four units: a methanol reformer with a catalytic combustor, a CO remover and two vaporizers. The dimensions of the microreactor were estimated by thermal simulation in order to achieve the required reaction temperature of each unit. In this study, the glass multi-layered microreactor was produced using anodic bonding. The number of glass pieces of which the microreactor was composed was 13. The experimental temperature of each unit, as well as the heat loss, for a methanol reformer of temperatures at 280{sup o}C was measured and compared with the results from thermal simulation. (author)

  19. Preparation of Biomorphic SiC/C Ceramics from Pine Wood via Supercritical Ethanol Infiltration

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Biomorphic (wood derived) carbide ceramics with an overall composition in the SiC/C was produced by supercritical ethanol infiltration of low viscosity tetraethylorthosilicate/supercritical ethanol into biologically derived carbon templates (CB-templates) and in situ hydrolysis into Si(OH)4-gel, the Si(OH)4-gel was calcined at 1400℃ to promote the polycondensation of Si(OH)4-gel into SiO2-phase and then carbonthermal reduction of the SiO2 with the biocarbon template into highly porous, biomorphic SiC/C ceramics. The phases and morphology conversion mechanism of resulting porous SiC/C ceramics have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR). Experimental results showed that the biomorphic cellular morphology of pinewood charcoal was remained in the porous SiC/C ceramic with high precision that consisted of β-SiC with minority of α-SiC and the remain free carbon existed in amorphous phase.

  20. Water/oil repellent property of polyester fabrics after supercritical carbon dioxide finishing

    Directory of Open Access Journals (Sweden)

    Xu Yan-Yan

    2015-01-01

    Full Text Available The strong permeability and driving force of supercritical carbon dioxide renders it an ideal medium for fabrics finishing. This paper is to use supercritical carbon dioxide medium with a solution of organic fluorine to fabricate water/oil repellent polyester fabrics. A series of characterization methods including Fourier transform infrared spectrometry, energy dispersive spectrometry, and scanning electron microscopy were carried out to evaluate the fabrics finishing. Fourier transform infrared spectrometry showed that the transmittance peak appeared at 1202.4 and 1147.4 cm-1, indicating the presence of -CF2- group on the surface of polyester fabrics. The results of energy dispersive spectrometer and scanning electron microscopy showed that the fluorine was evenly distributed on the fibers surface. In addition, a series of physical properties were detected, including contact angel, air permeability, breaking strength, and wearing resistance. The average water and hexadecane contact angles were 147.58° and 143.78°, respectively. Compared with the initial fabrics, the treated one has little change in air permeability, while its strength increased greatly. The treated fabrics gained good water/oil repellent properties while keeping good air permeability and improving mechanical property.

  1. Synthesis and Characterization of Cobalt-Carbon Core-Shell Microspheres in Supercritical Carbon Dioxide System

    Institute of Scientific and Technical Information of China (English)

    Jun-song Yang; Qian-wang Chen

    2008-01-01

    The synthesis of cobalt-carbon core-shell microspheres in supercritical carbon dioxide system was investigated. Cobalt-carbon core-shell microspheres with diameter of about 1μm were prepared at 350℃ for 12 h in a closed vessel containing an appropriate amount of bis(cyclopentadienyl)cobalt powder and dry ice.Characterization by a variety of techniques,including X-ray powder diffraction,X-ray photoelectron spectroscopy,Transmission electron microscope,Fourier transform infrared spectrum and Raman spectroscopy analysis reveals that each cobalt-carbon core-shell microsphere is made up of an amorphous cobalt core with diameter less than 1 μm and an amorphous carbon shell with thickness of about 200 nm.The possible growth mechanism of cobalt-carbon core-shell microspheres is discussed,based on the pyrolysis of bis(cyclopentadienyl)cobalt in supercritical carbon dioxide and the deposition of carbon or carbon clusters with odd electrons on the surface of magnetic cobalt cores due to magnetic attraction.Magnetic measurements show 141.41 emu/g of saturation magnetization of a typical sample,which is lower than the 168 emu/g of the corresponding metal cobalt bulk material.This is attributed to the considerable mass of the carbon shell and amorphous nature of the magnetic core.Control of magnetism in the cobalt-carbon core-shell microspheres was achieved by annealing treatments.

  2. Solid-state flurbiprofen and methyl-β-cyclodextrin inclusion complexes prepared using a single-step, organic solvent-free supercritical fluid process.

    Science.gov (United States)

    Rudrangi, Shashi Ravi Suman; Kaialy, Waseem; Ghori, Muhammad U; Trivedi, Vivek; Snowden, Martin J; Alexander, Bruce David

    2016-07-01

    The aim of this study was to enhance the apparent solubility and dissolution properties of flurbiprofen through inclusion complexation with cyclodextrins. Especially, the efficacy of supercritical fluid technology as a preparative technique for the preparation of flurbiprofen-methyl-β-cyclodextrin inclusion complexes was evaluated. The complexes were prepared by supercritical carbon dioxide processing and were evaluated by solubility, differential scanning calorimetry, X-ray powder diffraction, scanning electron microscopy, practical yield, drug content estimation and in vitro dissolution studies. Computational molecular docking studies were conducted to study the possibility of molecular arrangement of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin. The studies support the formation of stable molecular inclusion complexes between the drug and cyclodextrin in a 1:1 stoichiometry. In vitro dissolution studies showed that the dissolution properties of flurbiprofen were significantly enhanced by the binary mixtures prepared by supercritical carbon dioxide processing. The amount of flurbiprofen dissolved into solution alone was very low with 1.11±0.09% dissolving at the end of 60min, while the binary mixtures processed by supercritical carbon dioxide at 45°C and 200bar released 99.39±2.34% of the drug at the end of 30min. All the binary mixtures processed by supercritical carbon dioxide at 45°C exhibited a drug release of more than 80% within the first 10min irrespective of the pressure employed. The study demonstrated the single step, organic solvent-free supercritical carbon dioxide process as a promising approach for the preparation of inclusion complexes between flurbiprofen and methyl-β-cyclodextrin in solid-state.

  3. Methanol in diesel engines with increased efficiency by means of methanol dissociation. Methanol in dieselmotoren met verhoogd rendement door middel van methanoldissociatie

    Energy Technology Data Exchange (ETDEWEB)

    Ter Rele, R.R.J.; Van Asch, R.; Van der Does, C.

    1988-06-01

    The methanol dissociation project had the purpose to demonstrate a system in a diesel engine in which a part of the diesel fuel is replaced by dissociated methanol. The demonstration has been executed in a DAF 615 diesel engine under pressure. A previous developed diesel mixing operating system provided for correct gas quantity for all the load conditions. The Dutch State Mines (DSM) did research on the most appropriate catalyst and designed a methanol dissociation reactor. Descriptions of the fuel system, methanol evaporator and methanol dissociation reactor are given. Results of several measurements are presented: measurements on the diesel motor as a standard design, measurements for evaporated methanol as a substitute fuel for diesel and measurements for dissociated methanol or synthetic dissociation gas as substitute fuels. Differences between diesel and the substitutes are discussed. 12 figs., 4 ills., 3 tabs., 10 apps.

  4. Electrodeposited Pt and Pt-Sn nanoparticles on Ti as anodes for direct methanol fuel cells

    Institute of Scientific and Technical Information of China (English)

    Hanaa B HASSAN

    2009-01-01

    Electro-oxidation of methanol was studied on titanium supported nanocrystallite Pt and Ptx-Sny catalysts prepared by electrodeposition techniques. Their electro-catalytic activities were studied in 0.5mol/L H2SO4 and compared to those of a smooth Pt, Pt/Pt and Pt-Sn/Pt electrodes. Platinum was deposited on Ti by galvanostatic and potentiostatic techniques. X-ray diffractometer (XRD) and energy dispersive X-ray (EDX) techniques were applied in order to investigate the chemical composition and the phase structure of the modified electrodes. Scanning electron microscopy (SEM) was used to characterize the surface morphology and to correlate the results obtained from the two electrochemical deposition methods. Results show that modified Pt/Ti electrodes prepared by the two methods have comparable performance and enhanced catalytic activity towards methanol electro-oxidation compared to Pt/Pt and smooth Pt electrodes. Steady state Tafel plots experiments show a higher rate of methanol oxidation on a Pt/Ti catalyst than that on a smooth Pt. Introduction of a small amount of Sn deposited with Pt improves the catalytic activity and the stability of prepared electrode with time as indicated from the cyclic votlammetry and the chronoamperometric experiments. The effect of variations in the composition for binary catalysts of the type Ptx-Sny/Ti towards the methanol oxidation reaction is reported. Consequently, the Ptx-Sny/Ti (x∶y (8∶1), molar ratio) catalyst is a very promising one for methanol oxidation.

  5. Methanol electro-oxidation on Pt/C modified by polyaniline nanofibers for DMFC applications

    Energy Technology Data Exchange (ETDEWEB)

    Zhiani, Mohammad; Rezaei, Behzad; Jalili, Jalal [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran)

    2010-09-15

    In the present study, in order to achieve an inexpensive tolerable anode catalyst for direct methanol fuel cell applications, a composite of polyaniline nanofibers and Pt/C nano-particles, identified by PANI/Pt/C, was prepared by in-situ electropolymerization of aniline and trifluoromethane sulfonic acid on glassy carbon. The effect of synthesized PANI nanofibers in methanol electrooxidation reaction was compared by bare Pt/C by different electrochemical methods such as; cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronoamperometry. Scanning electron microscopy (SEM) was also employed to morphological study of the modified catalyst layer. The test results reveal that introduction of PANI nanofibers within catalyst layer improves the catalyst activity in methanol oxidation, hinders and prevents catalyst from more poisoning by intermediate products of methanol oxidation and improves the mechanical properties of the catalyst layer. SEM images also indicate that PANI nanofibers placed between platinum particles and anchor platinum particles and alleviate the Pt migration during methanol electrooxidation. (author)

  6. DETECTION OF 36 GHz CLASS I METHANOL MASER EMISSION TOWARD NGC 253

    Energy Technology Data Exchange (ETDEWEB)

    Ellingsen, Simon P. [School of Physical Sciences, University of Tasmania, Hobart, Tasmania (Australia); Chen, Xi; Qiao, Hai-Hua; Baan, Willem; An, Tao; Li, Juan [Shanghai Astronomical Observatory, Chinese Academy of Sciences, Shanghai 200030 (China); Breen, Shari L., E-mail: Simon.Ellingsen@utas.edu.au [CSIRO Astronomy and Space Science, Australia Telescope National Facility, P.O. Box 76, Epping, NSW 1710 (Australia)

    2014-08-01

    We have used the Australia Telescope Compact Array to search for emission from the 4{sub –1} → 3{sub 0} E transition of methanol (36.2 GHz) toward the center of the nearby starburst galaxy NGC 253. Two regions of emission were detected, offset from the nucleus along the same position angle as the inner spiral arms. The emission is largely unresolved on a scale of 5'', has a FWHM line width of <30 km s{sup –1}, and an isotropic luminosity orders of a magnitude larger than that observed in any Galactic star formation region. These characteristics suggest that the 36.2 GHz methanol emission is most likely a maser, although observations with higher angular and spectral resolution are required to confirm this. If it is a maser, this represents the first detection of a class I methanol maser outside the Milky Way. The 36.2 GHz methanol emission in NGC 253 has more than an order of magnitude higher isotropic luminosity than the widespread emission recently detected toward the center of the Milky Way. If emission from this transition scales with the nuclear star formation rate, then it may be detectable in the central regions of many starburst galaxies. Detection of methanol emission in ultra-luminous infrared galaxies would open up a new tool for testing for variations in fundamental constants (particularly the proton-to-electron mass ratio) on cosmological scales.

  7. Pd-gate MOS sensor for detection of methanol and propanol

    Institute of Scientific and Technical Information of China (English)

    Preeti Pandey; J.K.Srivastava; V.N.Mishra; R.Dwivedi

    2011-01-01

    The present paper focused on the detection of methanol and propanol using Pd-gate metal-oxide-semiconductor(MOS)sensor.Surface morphology and composition of the gate film were studied by scanning electron microscopy(SEM)and atomic force microscopy(AFM).The response of the sensor for propanol and methanol was measured as shift in capacitance-voltage(C-V) and conductance-voltage(G-V) curves of the MOS structure.The sensitivity of the sensor towards methanol was found to be greater than that towards propanol.It was 58.2% for methanol and 32% for propanol(at 0.6 V,1 MHz)in terms of capacitance measurements,while in terms of conductance results the sensitivity was found to be 57.2% for methanol and 38.9% for propanol at 1 kHz.The discontinuities or cracks present in the microstructure of the gate material are believed to be mainly responsible for the high sensitivity of the sensor,going with the decomposition of gas molecules and subsequent hydrogen permeation through Pd.

  8. Preliminary Design of In-Pile Supercritical Pressurized Water Test Loop

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>Based on two proven technologies, current light water reactors (LWRs) and the supercritical coal-fired power plants, the supercritical water-cooled reactor (SCWR) is one of the six Generation-Ⅳ

  9. SUPERCRITICAL FLUID EXTRACTION OF POLYCYCLIC AROMATIC HYDROCARBON MIXTURES FROM CONTAMINATED SOILS

    Science.gov (United States)

    Highly contaminated (with PAHs) topsoils were extracted with supercritical CO2 to determine the feasibility and mechanism of supercritical fluid extraction (SFE). Effect of SCF density, temperature, cosolvent type and amount, and of slurrying the soil with water were ...

  10. Engineering Escherichia coli for methanol conversion

    NARCIS (Netherlands)

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-01-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy

  11. Methanol emission from low mass protostars

    CERN Document Server

    Maret, S; Tielens, A G G M; Caux, E; Le Floc'h, B; Faure, A; Castets, A; Flower, D R

    2005-01-01

    We present observations of methanol lines in a sample of Class 0 low mass protostars. Using a 1-D radiative transfer model, we derive the abundances in the envelopes. In two sources of the sample, the observations can only be reproduced by the model if the methanol abundance is enhanced by about two order of magnitude in the inner hot region of the envelope. Two other sources show similar jumps, although at a lower confidence level. The observations for the other three sources are well reproduced with a constant abundance, but the presence of a jump cannot be ruled out. The observed methanol abundances in the warm gas around low mass protostars are orders of magnitude higher than gas phase chemistry models predict. Hence, in agreement with other evidences, this suggest that the high methanol abundance reflects recent evaporation of ices due to the heating by the newly formed star. The observed abundance ratios of CH3 OH, H2 CO, and CO are in good agreement with grain surface chemistry models. However, the abs...

  12. Metacridamide B methanol-d4 monosolvate

    Science.gov (United States)

    The title compound was extracted from conidia of the fungus Metarhizium acridum. Crystals were obtained as a methanol-d4 solvate. The tail part of the 4-methylhexan-2-yl group exhibits disorder over two positions, with an occupancy ratio of 0.682 (9):0.318 (9). The crystal structure confirms the abs...

  13. Methanol and acetaldehyde fluxes over ryegrass

    Science.gov (United States)

    Custer, Thomas; Schade, Gunnar

    2007-09-01

    Oxygenated volatile organic compounds (OVOCs) play an active role in tropospheric chemistry but our knowledge concerning their release and ultimate fate is limited. However, the recent introduction of Proton Transfer Reaction Mass Spectrometry (PTRMS) has improved our capability to make direct field observations of OVOC mixing ratios and fluxes. We used PTRMS in an eddy covariance setup to measure selected OVOC exchange rates above a well-characterized agricultural plot in Northern Germany. In fall 2003, mixing ratios of methanol and acetaldehyde 2 m above the field ranged from 1 to 10 and 0.4 to 2.1 ppb, respectively, well correlated with one another. Fluxes of both gases were followed for growing Italian ryegrass (Lolium multiflorum) over a significant portion of its life cycle. Diurnally fluctuating emissions of methanol and very small acetaldehyde fluxes were observed up to the cutting and removal of the grass. Methanol emissions were exponentially related to ambient temperatures and appeared to be higher during the grass' rapid leaf area expansion and after a rain event. Acetaldehyde exchanges averaged over the whole period indicated very slow deposition. Our measurements confirm previous, similar results, as well as presumptions that grasses are comparatively low methanol emitters compared to non-grass species.

  14. Antihyperlipidemic effect of Casearia sylvestris methanolic extract.

    Science.gov (United States)

    Schoenfelder, Tatiana; Pich, Claus T; Geremias, Reginaldo; Avila, Silvio; Daminelli, Elaine N; Pedrosa, Rozangela C; Bettiol, Jane

    2008-09-01

    Casearia sylvestris methanolic extract (MCE) was screened at doses of 125-500 mg/kg for its antihyperlipidemic activity. The antihyperlipidemic effect was evaluated in olive oil-loaded mice. Acute treatment caused inhibition in the triglyceride (TG) and serum lipase elevation-induced by 5 ml/kg of olive oil.

  15. Engineering Escherichia coli for methanol conversion

    NARCIS (Netherlands)

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-01-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy

  16. Parameters affecting methanol utilization by yeasts

    Energy Technology Data Exchange (ETDEWEB)

    Foda, M.S.; El-Masry, H.G.

    1981-01-01

    Screening of 28 yeast cultures, representing 22 species of various yeasts, with respect to their capabilities to assimilate methanol, has shown that this property was mostly found in certain species of the two genera Hansenula and Candida. When methanol was used as a sole carbon source for a methanol-adapted strain of Hansenula polymorpha, a linear yield response could be obtained with increasing alcohol up to 2% concentration. The amount of inoculum proved to be the decisive factor in determining a priori the ability of the organism to grow at 6% methanol as final concentration. The optimum pH values for growth ranged between 4.5-5.5 with no growth at pH 6.5 or higher. A marked growth stimulation was obtained when the medium was supplied with phosphate up to 0.08 M as final concentration. Within the nitrogen sources tested, corn steep liquor concentrate gave the highest yield of cells. The significance of the obtained results are discussed with reference to feasibilities of application.

  17. Synthesis and Optimization of a Methanol Proces

    DEFF Research Database (Denmark)

    Grue, J.; Bendtsen, Jan Dimon

    2003-01-01

    In the present paper, a simulation model for a methanol process is proposed. The objective is to develop a model for flowsheet optimization, which requires simple thermodynamic and unit operation models. Simplified thermodynamic models are combined with a more advanced model for the rate of react...

  18. 喷油脉宽对电控汽油机燃用M85甲醇汽油的影响%Effects of Fuel Injection Pulse on an Electronically Controlled Gasoline Engine Fueled with M85 Methanol-gasoline Blends

    Institute of Scientific and Technical Information of China (English)

    宋建桐; 朱清江

    2011-01-01

    为了在电控汽油机上优化M85甲醇汽油的应用,利用发动机台架试验,分析了电控汽油机直接燃用M85的主要问题,并通过放大喷油脉宽,增加M85甲醇汽油的喷油量来改善发动机性能.试验结果表明:与燃用汽油相比,喷油脉宽放大1.3倍时,发动机燃用M85甲醇汽油的功率和扭矩分别平均降低了6.83%和7.15%;小时燃油消耗量与有效燃油消耗率增大,但有效能耗平均降低6%;CO和HC排放分别平均降低11.28%和0.64%;NOx排放平均增加55.56%.%In order to optimize the application of M85 methanol-gasoline blends for electronically controlled engine, the problems were analyzed by bench tests of an engine when the electronically controlled engine was fueled directly with M85. The fuel injection pulse width signal is extended in order to increase injection quantity of M85 and improve the performance of engine fueled with M85. Experimental result shows that compared with gasoline fuel, with the injection pulse width amplified 1. 3 times, M85 has, on average, a reduction of 6. 83% and 7.15% for power and torque respectively, a reduction of 6% for effective energy consumption rate although the fuel consumption per hour and brake specific fuel consumption increased, a reduction of 11.28% and Q.64% for CO emission and HC emission respectively, and an increase of 55.56% for NO, emission.

  19. Optimized fuel cell grade hydrogen from methanol

    Science.gov (United States)

    Choi, Yongtaek

    2003-10-01

    To evaluate reaction rates liar making hydrogen from methanol, kinetic studies of methanol decomposition, methanol steam reforming, water gas shift reaction, and CO selective oxidation have been performed. These reactions were studied in a micro reactor testing unit using a commercial Cu-ZnO/Al2O3 catalyst for the first three reactions and Pt-Fe/gamma-alumina catalyst for the last reaction. The activity tests were performed between 120˜325°C and atmospheric pressure with a range of feed rates and compositions. For methanol decomposition, water addition to the feed increased the yield of hydrogen and reduced the formation of by-products. XPS analysis of used catalyst samples and time on-stream data showed that the Cu2+ oxidation state of copper favors methanol decomposition. A simplified reaction network of 5 elementary reactions was proposed and all five rate expressions were obtained using non-linear least squares optimization, numerical integration of a one-dimensional PFR model, and extensive experimental data. Similar numerical analysis was carried out to obtain the rate expressions for methanol steam reaction, the water gas shift reaction, and CO selective oxidation. For the kinetics of the water gas shift reaction, an empirical rate expression was obtained from the experimental data. Based on a review of published work on the WGS reaction mechanism, our study found that a rate expression derived from a regenerative mechanism and another rate expression derived from adsorptive mechanism fit the experimental data equally well. For the kinetics of CO preferential oxidation, a reaction model in which three reactions (CO oxidation, H2 oxidation and the WGS reaction) occur simultaneously was chosen to predict the reactor performance. In particular the reverse water gas shift reaction had an important role when fitting the experimental data precisely and explained the selectivity decrease at higher reaction temperatures. Combining the three reactors and several

  20. Selectivity of Direct Methanol Fuel Cell Membranes

    Directory of Open Access Journals (Sweden)

    Antonino S. Aricò

    2015-11-01

    Full Text Available Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK, new generation perfluorosulfonic acid (PFSA systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC. The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2. This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115.

  1. Selectivity of Direct Methanol Fuel Cell Membranes

    Science.gov (United States)

    Aricò, Antonino S.; Sebastian, David; Schuster, Michael; Bauer, Bernd; D’Urso, Claudia; Lufrano, Francesco; Baglio, Vincenzo

    2015-01-01

    Sulfonic acid-functionalized polymer electrolyte membranes alternative to Nafion® were developed. These were hydrocarbon systems, such as blend sulfonated polyetheretherketone (s-PEEK), new generation perfluorosulfonic acid (PFSA) systems, and composite zirconium phosphate–PFSA polymers. The membranes varied in terms of composition, equivalent weight, thickness, and filler and were investigated with regard to their methanol permeation characteristics and proton conductivity for application in direct methanol fuel cells. The behavior of the membrane electrode assemblies (MEA) was investigated in fuel cell with the aim to individuate a correlation between membrane characteristics and their performance in a direct methanol fuel cell (DMFC). The power density of the DMFC at 60 °C increased according to a square root-like function of the membrane selectivity. This was defined as the reciprocal of the product between area specific resistance and crossover. The power density achieved at 60 °C for the most promising s-PEEK-based membrane-electrode assembly (MEA) was higher than the benchmark Nafion® 115-based MEA (77 mW·cm−2 vs. 64 mW·cm−2). This result was due to a lower methanol crossover (47 mA·cm−2 equivalent current density for s-PEEK vs. 120 mA·cm−2 for Nafion® 115 at 60 °C as recorded at OCV with 2 M methanol) and a suitable area specific resistance (0.15 Ohm cm2 for s-PEEK vs. 0.22 Ohm cm2 for Nafion® 115). PMID:26610582

  2. Supercritical fluid reactions for coal processing. Quarterly progress report, April 1, 1996--June 30, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Eckert, C.A.

    1996-11-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as the model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane.

  3. Supercritical fluid reactions for coal processing. Quarterly report, January 1, 1996--March 31, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Eckert, C.A.

    1996-10-01

    Exciting opportunities exist for the application of supercritical fluid (SCF) reactions for the pre-treatment of coal. Utilizing reactants which resemble the organic nitrogen containing components of coal, we propose to develop a method to tailor chemical reactions in supercritical fluid solvents for the specific application of coal denitrogenation. The tautomeric equilibrium of a Schiff base was chosen as the model system and was investigated in supercritical ethane and cosolvent modified supercritical ethane.

  4. An Analysis of Methanol and Hydrogen Production via High-Temperature Electrolysis Using the Sodium Cooled Advanced Fast Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Shannon M. Bragg-Sitton; Richard D. Boardman; Robert S. Cherry; Wesley R. Deason; Michael G. McKellar

    2014-03-01

    Integration of an advanced, sodium-cooled fast spectrum reactor into nuclear hybrid energy system (NHES) architectures is the focus of the present study. A techno-economic evaluation of several conceptual system designs was performed for the integration of a sodium-cooled Advanced Fast Reactor (AFR) with the electric grid in conjunction with wind-generated electricity. Cases in which excess thermal and electrical energy would be reapportioned within an integrated energy system to a chemical plant are presented. The process applications evaluated include hydrogen production via high temperature steam electrolysis and methanol production via steam methane reforming to produce carbon monoxide and hydrogen which feed a methanol synthesis reactor. Three power cycles were considered for integration with the AFR, including subcritical and supercritical Rankine cycles and a modified supercritical carbon dioxide modified Brayton cycle. The thermal efficiencies of all of the modeled power conversions units were greater than 40%. A thermal efficiency of 42% was adopted in economic studies because two of the cycles either performed at that level or could potentially do so (subcritical Rankine and S-CO2 Brayton). Each of the evaluated hybrid architectures would be technically feasible but would demonstrate a different internal rate of return (IRR) as a function of multiple parameters; all evaluated configurations showed a positive IRR. As expected, integration of an AFR with a chemical plant increases the IRR when “must-take” wind-generated electricity is added to the energy system. Additional dynamic system analyses are recommended to draw detailed conclusions on the feasibility and economic benefits associated with AFR-hybrid energy system operation.

  5. Corrosion of combustion-synthesized {beta}-SiAlONs in supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Yi Xuemei [Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Yamauchi, Akira; Kurokawa, Kazuya [Center for Advanced Research of Energy and Materials, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan); Akiyama, Tomohiro, E-mail: takiyama@eng.hokudai.ac.jp [Center for Advanced Research of Energy and Materials, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628 (Japan)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer The corrosion of {beta}-Si{sub 6-z}Al{sub z}O{sub z}N{sub 8-z}s (z = 1, 2, and 3) has been investigated in SCW under 400 Degree-Sign C/35 MPa for 100 h. Black-Right-Pointing-Pointer The corrosion behavior of these materials is studied using XRD, SEM, and EDS. Black-Right-Pointing-Pointer The reaction mechanism of {beta}-Si{sub 6-z}Al{sub z}O{sub z}N{sub 8-z}s in supercritical water is proposed. Black-Right-Pointing-Pointer The results in this study could present a valuable example for similar studies. - Abstract: The corrosion of {beta}-Si{sub 6-z}Al{sub z}O{sub z}N{sub 8-z}s (z = 1, 2, and 3) prepared by combustion synthesis (CS) followed by spark plasma sintering (SPS) was investigated in supercritical water at 400 Degree-Sign C/30 MPa for 100 h. The corrosion behavior was studied by means of gravimetry, X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive X-ray spectrometer (EDS). The mass loss and corroded layer decreased with the increasing in z value, and the results of XRD showed the oxide formed on {beta}-SiAlONs (z = 1, 2, and 3) is aluminum silicate (Al{sub 2}SiO{sub 5}). Finally, we proposed the reaction mechanism of these materials in supercritical water.

  6. Control of pore size and structure of tissue engineering scaffolds produced by supercritical fluid processing

    Directory of Open Access Journals (Sweden)

    H Tai

    2007-12-01

    Full Text Available Tissue engineering scaffolds require a controlled pore size and structure to host tissue formation. Supercritical carbon dioxide (scCO2 processing may be used to form foamed scaffolds in which the escape of CO2 from a plasticized polymer melt generates gas bubbles that shape the developing pores. The process of forming these scaffolds involves a simultaneous change in phase in the CO2 and the polymer, resulting in rapid expansion of a surface area and changes in polymer rheological properties. Hence, the process is difficult to control with respect to the desired final pore size and structure. In this paper, we describe a detailed study of the effect of polymer chemical composition, molecular weight and processing parameters on final scaffold characteristics. The study focuses on poly(DL-lactic acid (PDLLA and poly(DL-lactic acid-co-glycolic acid (PLGA as polymer classes with potential application as controlled release scaffolds for growth factor delivery. Processing parameters under investigation were temperature (from 5 to 55oC and pressure (from 60 to 230 bar. A series of amorphous PDLLA and PLGA polymers with various molecular weights (from 13 KD to 96 KD and/or chemical compositions (the mole percentage of glycolic acid in the polymers was 0, 15, 25, 35 and 50 respectively were employed. The resulting scaffolds were characterised by optical microscopy, scanning electron microscopy (SEM, and micro X-ray computed tomography (µCT. This is the first detailed study on using these series polymers for scaffold formation by supercritical technique. This study has demonstrated that the pore size and structure of the supercritical PDLLA and PLGA scaffolds can be tailored by careful control of processing conditions.

  7. Methanol poisoning. VI. Role of folic acid in the production of methanol poisoning in the rat

    Energy Technology Data Exchange (ETDEWEB)

    Makar, A.B. (Alexandria Univ., Egypt); Tephly, T.R.

    1977-05-01

    Methanol poisoning is well known to occur in humans but does not develop in common laboratory animals such as the rat. Rodents display neither metabolic acidosis nor ocular toxicity after methanol treatment, findings that commonly result in humans and that have recently been described in the monkey. Since methanol administration in the monkey leads to marked accumulation of formic acid and metabolic acidosis, experiments were devised to reduce formate metabolism in the rat and thereby study whether methanol administration would lead to the accumulation of formic acid and acidosis in that species. Several methods were employed to induce a state of folate deficiency in the rat, a prerequisite to producing a decrease in formate oxidation to CO/sub 2/ in that species. Rats placed on a folate-deficient diet for 10-12 wk showed a marked decrease in formate oxidation and a marked sensitivity to methanol poisoning, as evidenced by high blood formate levels and marked decreases in blood pH. Treatment of rats with methotrexate was relatively ineffective in inducing decreases in formate oxidation, but in rats fed a folate-deficient diet for 9 days and injected once daily for 9 days with 1 mg/kg methotrexate, a significant elevation of blood formate and decrease in blood pH was observed. In rats that were acidotic following methanol administration no accumulation of formaldehyde was observed. These results indicate that it is possible to sensitize the rat to methanol poisoning by reducing its capacity to oxidize formate. They also show that once the rat is susceptible to methanol poisoning, metabolic acidosis and formate accumulation occur without the accumulation of formaldehyde.

  8. Effect of Ni Core Structure on the Electrocatalytic Activity of Pt-Ni/C in Methanol Oxidation

    Directory of Open Access Journals (Sweden)

    Vladimir Linkov

    2013-07-01

    Full Text Available Methanol oxidation catalysts comprising an outer Pt-shell with an inner Ni-core supported on carbon, (Pt-Ni/C, were prepared with either crystalline or amorphous Ni core structures. Structural comparisons of the two forms of catalyst were made using transmission electron microscopy (TEM, X-ray diffraction (XRD and X-ray photoelectron spectroscopy (XPS, and methanol oxidation activity compared using CV and chronoamperometry (CA. While both the amorphous Ni core and crystalline Ni core structures were covered by similar Pt shell thickness and structure, the Pt-Ni(amorphous/C catalyst had higher methanol oxidation activity. The amorphous Ni core thus offers improved Pt usage efficiency in direct methanol fuel cells.

  9. Multiple hydrogen bonding in excited states of aminopyrazine in methanol solution: time-dependent density functional theory study.

    Science.gov (United States)

    Chai, Shuo; Yu, Jie; Han, Yong-Chang; Cong, Shu-Lin

    2013-11-01

    Aminopyrazine (AP) and AP-methanol complexes have been theoretically studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The excited-state hydrogen bonds are discussed in detail. In the ground state the intermolecular multiple hydrogen bonds can be formed between AP molecule and protic solvents. The AP monomer and hydrogen-bonded complex of AP with one methanol are photoexcited initially to the S2 state, and then transferred to the S1 state via internal conversion. However the complex of AP with two methanol molecules is directly excited to the S1 state. From the calculated electronic excited energies and simulated absorption spectra, we find that the intermolecular hydrogen bonds are strengthened in the electronic excited states. The strengthening is confirmed by the optimized excited-state geometries. The photochemical processes in the electronic excited states are significantly influenced by the excited-state hydrogen bond strengthening.

  10. Enhancement of the dissolution rate and bioavailability of fenofibrate by a melt-adsorption method using supercritical carbon dioxide

    Directory of Open Access Journals (Sweden)

    Cha KH

    2012-10-01

    Full Text Available Kwang-Ho Cha,1,3 Kyung-Jin Cho,3 Min-Soo Kim,4 Jeong-Soo Kim,3 Hee Jun Park,1,3 Junsung Park,1,3 Wonkyung Cho,1,3 Jeong-Sook Park,3 Sung-Joo Hwang1,21Yonsei Institute of Pharmaceutical Sciences, 2College of Pharmacy, Yonsei University, Incheon, Republic of Korea; 3College of Pharmacy, Chungnam National University, Daejeon, Republic of Korea; 4Department of Pharmaceutical Engineering, Inje University, Gimhae, Republic of KoreaBackground: The aim of this study was to enhance the bioavailability of fenofibrate, a poorly water-soluble drug, using a melt-adsorption method with supercritical CO2.Methods: Fenofibrate was loaded onto Neusilin® UFL2 at different weight ratios of fenofibrate to Neusilin UFL2 by melt-adsorption using supercritical CO2. For comparison, fenofibrate-loaded Neusilin UFL2 was prepared by solvent evaporation and hot melt-adsorption methods. The fenofibrate formulations prepared were characterized by differential scanning calorimetry, powder x-ray diffractometry, specific surface area, pore size distribution, scanning electron microscopy, and energy-dispersive x-ray spectrometry. In vitro dissolution and in vivo bioavailability were also investigated.Results: Fenofibrate was distributed into the pores of Neusilin UFL2 and showed reduced crystal formation following adsorption. Supercritical CO2 facilitated the introduction of fenofibrate into the pores of Neusilin UFL2. Compared with raw fenofibrate, fenofibrate from the prepared powders showed a significantly increased dissolution rate and better bioavailability. In particular, the area under the drug concentration-time curve and maximal serum concentration of the powders prepared using supercritical CO2 were 4.62-fold and 4.52-fold greater than the corresponding values for raw fenofibrate.Conclusion: The results of this study highlight the usefulness of the melt-adsorption method using supercritical CO2 for improving the bioavailability of fenofibrate.Keywords: fenofibrate

  11. Methanol production from Eucalyptus wood chips. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Fishkind, H.H.

    1982-06-01

    This feasibility study includes all phases of methanol production from seedling to delivery of finished methanol. The study examines: production of 55 million, high quality, Eucalyptus seedlings through tissue culture; establishment of a Eucalyptus energy plantation on approximately 70,000 acres; engineering for a 100 million gallon-per-day methanol production facility; potential environmental impacts of the whole project; safety and health aspects of producing and using methanol; and development of site specific cost estimates.

  12. Topics in Chemical Instrumentation--An Introduction to Supercritical Fluid Chromatography: Part 1: Principles and Instrumentation.

    Science.gov (United States)

    Palmieri, Margo D.

    1988-01-01

    Identifies the properties and characteristics of supercritical fluids. Discusses the methodology for supercritical fluid chromatography including flow rate, plate height, column efficiency, viscosity, and other factors. Reviews instruments, column types, and elution conditions. Lists supercritical fluid data for 22 compounds, mostly organic. (MVL)

  13. Novel strategy of using methyl esters as slow release methanol source during lipase expression by mut+ Pichia pastoris X33.

    Directory of Open Access Journals (Sweden)

    Arti Kumari

    Full Text Available One of the major issues with heterologous production of proteins in Pichia pastoris X33 under AOX1 promoter is repeated methanol induction. To obviate repeated methanol induction, methyl esters were used as a slow release source of methanol in lipase expressing mut+ recombinant. Experimental design was based on the strategy that in presence of lipase, methyl esters can be hydrolysed to release their products as methanol and fatty acid. Hence, upon break down of methyl esters by lipase, first methanol will be used as a carbon source and inducer. Then P. pastoris can switch over to fatty acid as a carbon source for multiplication and biomass maintenance till further induction by methyl esters. We validated this strategy using recombinant P. pastoris expressing Lip A, Lip C from Trichosporon asahii and Lip11 from Yarrowia lipolytica. We found that the optimum lipase yield under repeated methanol induction after 120 h was 32866 U/L, 28271 U/L and 21978 U/L for Lip C, Lip A and Lip 11 respectively. In addition, we found that a single dose of methyl ester supported higher production than repeated methanol induction. Among various methyl esters tested, methyl oleate (0.5% caused 1.2 fold higher yield for LipA and LipC and 1.4 fold for Lip11 after 120 h of induction. Sequential utilization of methanol and oleic acid by P. pastoris was observed and was supported by differential peroxisome proliferation studies by transmission electron microscopy. Our study identifies a novel strategy of using methyl esters as slow release methanol source during lipase expression.

  14. Novel strategy of using methyl esters as slow release methanol source during lipase expression by mut+ Pichia pastoris X33.

    Science.gov (United States)

    Kumari, Arti; Gupta, Rani

    2014-01-01

    One of the major issues with heterologous production of proteins in Pichia pastoris X33 under AOX1 promoter is repeated methanol induction. To obviate repeated methanol induction, methyl esters were used as a slow release source of methanol in lipase expressing mut+ recombinant. Experimental design was based on the strategy that in presence of lipase, methyl esters can be hydrolysed to release their products as methanol and fatty acid. Hence, upon break down of methyl esters by lipase, first methanol will be used as a carbon source and inducer. Then P. pastoris can switch over to fatty acid as a carbon source for multiplication and biomass maintenance till further induction by methyl esters. We validated this strategy using recombinant P. pastoris expressing Lip A, Lip C from Trichosporon asahii and Lip11 from Yarrowia lipolytica. We found that the optimum lipase yield under repeated methanol induction after 120 h was 32866 U/L, 28271 U/L and 21978 U/L for Lip C, Lip A and Lip 11 respectively. In addition, we found that a single dose of methyl ester supported higher production than repeated methanol induction. Among various methyl esters tested, methyl oleate (0.5%) caused 1.2 fold higher yield for LipA and LipC and 1.4 fold for Lip11 after 120 h of induction. Sequential utilization of methanol and oleic acid by P. pastoris was observed and was supported by differential peroxisome proliferation studies by transmission electron microscopy. Our study identifies a novel strategy of using methyl esters as slow release methanol source during lipase expression.

  15. Effect of methanol ratio in mixed solvents on optical properties and wettability of ZnO films by cathodic electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao; Xu, Kai; Jiang, Xishun; Yang, Lei; He, Gang; Song, Xueping [School of Physics and Material Science, Anhui University, Hefei 230601 (China); Sun, Zhaoqi, E-mail: szq@ahu.edu.cn [School of Physics and Material Science, Anhui University, Hefei 230601 (China); Lv, Jianguo, E-mail: lvjg1@163.com [School of Electronic and Information Engineering, Hefei Normal University, Hefei 230601 (China)

    2014-12-05

    Highlights: • Different surface morphologies of ZnO films were prepared by cathodic electrodeposition. • The surface morphologies are controlled through add different ratio methanol to electrolyte. • The morphology changes from nanorods with hexagonal structure to net-like nanostructure. • The wettability of films shows obvious change with increasing methanol ratio. • The maximum light-induced CA change has been observed with the methanol ratio of 0.8. - Abstract: ZnO thin films were prepared in the electrolyte with different methanol ratio by cathodic electrodeposition method. Microstructure, surface morphology, optical properties and wettability of the thin films were investigated by X-ray diffractometer, field-emission scanning electron microscope, ultraviolet–visible spectroscope, fluorescence spectrometer and water contact angle apparatus. Increase of methanol ratio in the solvents may restrain the (0 0 2) plane preferential orientation in some extent. Change of current density curves with the ratio of methanol in the solution play a vital role on electrochemical reaction kinetics, microstructure and/or surface morphology of ZnO thin films. With the methanol ratio increase from 0 to 0.8, the surface morphology changes from nanorods to net-like nanostructure. The adsorbed NO{sub 3}{sup −} ions on the polar planes hinder the crystal growth along the c-axis and redirect the growth direction along the nonpolar planes. The maximum and minimum band gaps have been obtained in the ZnO thin films with the methanol ratio of 0.4 and 0.6, respectively. Change of contact angle before UV irradiation may be related to surface morphology and oxygen vacancies. The maximum light-induced water contact angle change has been observed in the sample with the methanol ratio of 0.8. The results may be attributed to the higher surface roughness and net-like morphology.

  16. Simultaneous observation of water and class I methanol masers toward class II methanol maser sources

    CERN Document Server

    Kang, Hyunwoo; Byun, Do-Young; Lee, Seokho; Park, Yong-Sun

    2015-01-01

    We present a simultaneous single-dish survey of 22 GHz water maser and 44 GHz and 95 GHz class I methanol masers toward 77 6.7 GHz class II methanol maser sources, which were selected from the Arecibo methanol maser Galactic plane survey (AMGPS) catalog.Water maser emission is detected in 39 (51%) sources, of which 15 are new detections. Methanol maser emission at 44 GHz and 95 GHz is found in 25 (32%) and 19 (25%) sources, of which 21 and 13 sources are newly detected, respectively. We find 4 high-velocity (> 30 km/s) water maser sources, including 3 dominant blue- or redshifted outflows.The 95 GHz masers always appear with the 44 GHz maser emission. They are strongly correlated with 44 GHz masers in velocity, flux density, and luminosity, while they are not correlated with either water or 6.7 GHz class II methanol masers. The average peak flux density ratio of 95 GHz to 44 GHz masers is close to unity, which is two times higher than previous estimates. The flux densities of class I methanol masers are more ...

  17. The significance of peroxisomes in methanol metabolism in methylotrophic yeast

    NARCIS (Netherlands)

    Klei, Ida J. van der; Yurimoto, Hiroya; Sakai, Yasuyoshi; Veenhuis, Marten

    2006-01-01

    The capacity to use methanol as sole source of carbon and energy is restricted to relatively few yeast species. This may be related to the low efficiency of methanol metabolism in yeast, relative to that of prokaryotes. This contribution describes the details of methanol metabolism in yeast and focu

  18. A Methanol Intoxication Outbreak From Recreational Ingestion of Fracking Fluid.

    Science.gov (United States)

    Collister, David; Duff, Graham; Palatnick, Wesley; Komenda, Paul; Tangri, Navdeep; Hingwala, Jay

    2017-01-19

    Single-patient methanol intoxications are a common clinical presentation, but outbreaks are rare and usually occur in settings in which there is limited access to ethanol and methanol is consumed as a substitute. In this case report, we describe an outbreak of methanol intoxications that was challenging from a public health perspective and discuss strategies for managing such an outbreak.

  19. Acidities of Water and Methanol in Aqueous Solution and DMSO

    Science.gov (United States)

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  20. Acidities of Water and Methanol in Aqueous Solution and DMSO

    Science.gov (United States)

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…